Composition, cured product, and method for producing cured product

Abstract

To provide a composition which is excellent in depth curability, has a small shrinkage rate after curing, and can form a cured product having a high glass transition point, high dimensional stability, and remarkable adhesive force to aluminum or the like.SOLUTION: The composition contains a curable component, a sulfonium salt type photocationic polymerization initiator, and an iodonium salt type photocationic polymerization initiator. The curable component contains an alicyclic epoxy compound, at least one selected from an aromatic epoxy compound and an aliphatic epoxy compound, and an oxetane compound.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition, a cured product thereof, and a method for producing the cured product. [Background technology]

[0002] As a UV-curable adhesive composition, compositions containing epoxy resins have been studied because of their high adhesion and excellent water resistance, etc. For example, Patent Document 1 proposes an adhesive composition containing an oxetane compound, an alicyclic epoxy compound, an aromatic glycidyl ether epoxy compound, a photocationic polymerization initiator, and a thermal cationic polymerization initiator containing a tetrakis(pentafluorophenyl)borate compound. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2021-147584 Summary of the Invention [Problem to be solved by the invention]

[0004] However, a composition capable of forming a cured product having excellent deep curing properties, small cure shrinkage, a high glass transition temperature, dimensional stability, and excellent adhesive strength has not yet been obtained.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a composition that can form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, the present inventors have conducted extensive research into the causes of the above-mentioned problems and have found that the above-mentioned problems can be solved by a composition containing a combination of a specific curable component and a specific polymerization initiator.

[0007] That is, the present invention is As a curing component, an alicyclic epoxy compound; at least one selected from aromatic epoxy compounds and aliphatic epoxy compounds; an oxetane compound, As a polymerization initiator, a sulfonium salt-type cationic photopolymerization initiator; and an iodonium salt-type cationic photopolymerization initiator.

[0008] The present invention provides a cured product of the above composition. [Effects of the Invention]

[0009] According to the present invention, there can be provided a composition that can form a cured product having excellent deep curing properties, small cure shrinkage, a high glass transition point, and excellent dimensional stability and adhesive strength. DETAILED DESCRIPTION OF THE INVENTION

[0010] The present invention relates to a composition and a cured product thereof. The composition and cured product of the present invention will be described in detail below.

[0011] In the present disclosure, when a hydrogen atom in a group is substituted with a substituent, the number of carbon atoms in the group specifies the number of carbon atoms in the group after the substitution. For example, when a hydrogen atom in an alkyl group having 1 to 20 carbon atoms is substituted, the term "1 to 20 carbon atoms" refers to the number of carbon atoms after the hydrogen atom is substituted, not the number of carbon atoms before the hydrogen atom is substituted. Furthermore, in the present disclosure, the specification of the number of carbon atoms in a group in which a methylene group in a group with a specified number of carbon atoms is replaced with a divalent group specifies the number of carbon atoms in the group after the substitution.

[0012] A. Composition First, the composition of the present invention will be described. The composition contains, as curable components, an alicyclic epoxy compound, at least one selected from an aromatic epoxy compound and an aliphatic epoxy compound, and an oxetane compound; The composition is characterized in that it contains a sulfonium salt-type photocationic polymerization initiator and an iodonium salt-type photocationic polymerization initiator as the polymerization initiator. Each component constituting the composition will now be described.

[0013] A1. Curing component The curable component is a component that forms a cured product, and the composition is characterized by containing, as the curable component, an alicyclic epoxy compound, at least one selected from an aromatic epoxy compound and an aliphatic epoxy compound, and an oxetane compound.

[0014] (1) Alicyclic epoxy compounds The alicyclic epoxy compound is a compound having at least one alicyclic epoxy group in the molecule, i.e., a compound having a cycloalkene oxide structure, and may have multiple alicyclic epoxy groups in one molecule, or may have an epoxy group (epoxide) other than the alicyclic epoxy group. In addition, two or more of the alicyclic epoxy compounds may be used in combination.

[0015] The cycloalkene oxide structure may be a structure in which an aliphatic ring and an epoxy ring share a part of the ring structure, such as a cyclohexene oxide structure or a cyclopentene oxide structure, which is obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. In the present disclosure, a compound having an aromatic ring is also considered to fall under the category of the above-mentioned alicyclic epoxy compound, so long as it has a cycloalkene oxide structure.

[0016] In the present disclosure, any compound having an alicyclic epoxy group can be used without particular limitation. However, from the viewpoint of being able to form a cured product that has excellent deep curing properties and adhesive strength, it is preferable to include, for example, an alicyclic epoxy compound represented by the following general formula (A-1), (A-2), (A-3), (A-4), or (A-5).

[0017] [ka]

[0018] In general formula (A-1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, or an alkoxy group having from 1 to 20 carbon atoms.

[0019] [ka]

[0020] In general formula (A-2), R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 each independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, or an alkoxy group having from 1 to 20 carbon atoms.

[0021] [ka]

[0022] In general formula (A-3), R 31 , R 32 , R 33 , R 34 , R 35 , R 36 , R 37 , R 38 , R 39 , R 40 , R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 and R 48 each independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, or an alkoxy group having from 1 to 20 carbon atoms.

[0023] [ka]

[0024] In general formula (A-4), R 51 , R 52 , R 53 , R 54 , R 55 , R 56 , R 57 , R 58 , R 59 , R 60 , R 61 , R 62 , R 63 , R 64 , R 65 , R 66 , R 67 and R 68 each independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, or an alkoxy group having from 1 to 20 carbon atoms.

[0025] [ka]

[0026] (In general formula (A-5), R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R 79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 each independently represents a hydrogen atom, a halogen atom, an alkyl group having from 1 to 20 carbon atoms, or an alkoxy group having from 1 to 20 carbon atoms, Z represents a single bond, an alkylene group having 1 to 4 carbon atoms, a carbonyl group, an ether bond, a carbonate group, an amide group, or a group in which a plurality of these groups are linked together.

[0027] The "group in which a plurality of these are linked" for Z in the above general formula (A-5) can be a group in which a plurality of groups selected from alkylene groups, carbonyl groups, ether bonds, ester bonds, carbonate groups, and amide groups are linked together so that the groups other than alkylene groups are not adjacent to each other. Furthermore, two or more of the same type of groups may be combined, such as ester bond-alkylene group-ester bond-alkylene group.

[0028] R in the above general formula (A-1) 1 ~R 10 , R in the above general formula (A-2) 11 ~R 28 , R in the above general formula (A-3) 31 ~R 48 , R in the above general formula (A-4) 51 ~R 68 and R in the above general formula (A-5) 71 ~R 88Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0029] R in the above general formula (A-1) 1 ~R 10 , R in the above general formula (A-2) 11 ~R 28 , R in the above general formula (A-3) 31 ~R 48 , R in the above general formula (A-4) 51 ~R 68 and R in the above general formula (A-5) 71 ~R 88 Examples of the alkyl group having 1 to 20 carbon atoms, represented by the formula (I), include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, an octyl group, an isooctyl group, an oct ... Examples of such groups include a decyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an n-undecyl group, a 1-methyldecyl group, an n-dodecyl group, a 4-ethyloctyl group, a 1,3,5,7-tetramethyloctyl group, a tridecyl group, a 1-hexylheptyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, and an n-eicosyl group.

[0030] R in the above general formula (A-1) 1 ~R 10 , R in the above general formula (A-2) 11 ~R 28 , R in the above general formula (A-3) 31 ~R 48 , R in the above general formula (A-4) 51 ~R 68 and R in the above general formula (A-5) 71 ~R 88Examples of the alkoxy group having 1 to 20 carbon atoms represented by the formula (I) include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an amyloxy group, an isoamyloxy group, a tert-amyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, an isooctyloxy group, a 2-ethylhexyloxy group, a tert-octyloxy group, a nonyloxy group, an isononyloxy group, a decyloxy group, a methyl ... Examples of the alkyl group include an n-octyloxy group, an isodecyloxy group, an n-undecyloxy group, a 1-methyldecyloxy group, an n-dodecyloxy group, a 4-ethyloctyloxy group, a 1,3,5,7-tetramethyloctyloxy group, an n-tridecyloxy group, a 1-hexylheptyloxy group, an n-tetradecyloxy group, an n-pentadecyloxy group, an n-hexadecyloxy group, an n-heptadecyloxy group, an n-octadecyloxy group, and an n-eicosyloxy group.

[0031] The alkylene group having 1 to 4 carbon atoms represented by Z in the general formula (A-5) includes a group in which one hydrogen atom has been removed from an alkyl group having 1 to 4 carbon atoms. Examples of such an alkyl group include the R 1 ~R 10 Among the alkyl groups listed as alkyl groups represented by the formula (I), groups having a specific number of carbon atoms can be mentioned. Specific examples include a methylene group, a methylmethine group, an isopropylidene group, a dimethylmethine group, an ethylene group, a trimethylene group, and a tetramethylene group. Some or all of the hydrogen atoms in the alkylene group can be substituted with fluorine atoms.

[0032] The single bond is a direct bond between the carbon atoms linked to Z. Examples of compounds in which two cycloalkene oxide structures are bonded by such a single bond include compounds represented by the following general formula (A-6).

[0033] [ka]

[0034] Examples of methods for producing the compounds represented by the above general formulae (A-1) to (A-5) include the production method described in JP-A-2019-189844. Among the compounds represented by the general formula (A-1), commercially available examples include THI-DE (manufactured by ENEOS Corporation). Among the compounds represented by the general formula (A-2), commercially available examples include DE-102 (manufactured by ENEOS Corporation). Among the compounds represented by the above general formula (A-3), commercially available examples include DE-103 (manufactured by ENEOS Corporation). Among the compounds represented by the general formula (A-5), commercially available examples include DCA (manufactured by ADEKA Corporation), Celloxide 2021P, and Celloxide 2081 (all manufactured by Daicel Chemical Industries, Ltd.).

[0035] In the present disclosure, from the viewpoint of facilitating the formation of a cured product from the composition that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, the number of epoxy groups in the alicyclic epoxy compound is preferably 2 or more and 5 or less. More preferably, it is 2 or more and 3 or less, 2 is particularly preferred. The number of epoxy groups in the alicyclic epoxy compound includes the number of cycloalkene oxide structures and the number of epoxy groups other than the cycloalkene oxide structures.

[0036] In the present disclosure, from the viewpoint of facilitating the formation of a cured product from the composition that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, it is more preferable that the alicyclic epoxy compound includes at least one selected from the compounds represented by general formulas (A-1), (A-2), (A-3), (A-4), and (A-5). It is more preferable that the composition contains at least one compound selected from the compounds represented by the general formulas (A-1) and (A-5), It is particularly preferable that the compound represented by the above general formula (A-1) is contained.

[0037] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and can easily form a cured product having excellent dimensional stability and adhesive strength, in the above general formula (A-1), R 1 ~R 10 A compound in which at least one of the following is a hydrogen atom is preferred, R 1 ~R 10 More preferred are compounds in which two or more of the following are hydrogen atoms, R 1 ~R 10 More preferably, six or more of the above are hydrogen atoms, R 1 ~R 10 Particularly preferred are compounds in which seven or more of the following are hydrogen atoms, R 1 ~R 10 Among these, compounds in which eight or more of the above are hydrogen atoms are particularly preferred, R 1 ~R 10 More particularly preferred are compounds in which nine or more of the following are hydrogen atoms: R 1 ~R 10 The most preferred compound is one in which all of are hydrogen atoms.

[0038] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and a cured product having excellent dimensional stability and adhesive strength, R 71 ~R 88 A compound in which at least one of the following is a hydrogen atom is preferred, R 71 ~R 88 More preferred are compounds in which at least five of the R 71 ~R 88 More preferred are compounds in which at least nine of the following are hydrogen atoms: R 71 ~R 88Particularly preferred are compounds in which at least 13 of the R 71 ~R 88 Among these, compounds in which at least 17 of the following are hydrogen atoms are particularly preferred, Among them, R 71 ~R 88 The most preferred compound is one in which all of are hydrogen atoms.

[0039] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties and is easily able to form a cured product having a high glass transition temperature, Z in general formula (A-5) is preferably a single bond, an alkylene group having from 1 to 4 carbon atoms, an ester bond, or a group in which an alkylene group having from 1 to 4 carbon atoms is linked to an ester bond, More preferably, it is an alkylene group having from 1 to 4 carbon atoms, an ester bond, or a group in which an alkylene group having from 1 to 4 carbon atoms is linked to an ester bond, It is more preferable that the alkylene group has 1 to 4 carbon atoms, or a group in which an alkylene group having 1 to 4 carbon atoms is linked to an ester bond, An alkylene group having 1 to 4 carbon atoms is particularly preferred.

[0040] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The molecular weight of the alicyclic epoxy compound is It is preferably 100 or more and 500 or less, More preferably, it is 110 or more and 400 or less, More preferably, it is 120 or more and 300 or less, It is particularly preferable that the molecular weight is 130 or more and 250 or less, A value of 140 or more and 240 or less is particularly preferred.

[0041] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The epoxy equivalent of the alicyclic epoxy compound is Preferably, it is 30 g / eq or more and 250 g / eq or less, More preferably, it is 50 g / eq or more and 200 g / eq or less, It is more preferable that the content is 60 g / eq or more and 150 g / eq or less, It is particularly preferable that the molecular weight is 70 g / eq or more and 130 g / eq or less.

[0042] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, the content of the alicyclic epoxy compound is set to be: It is preferably 1 part by mass or more and 90 parts by mass or less, More preferably, the content is 20 parts by mass or more and 85 parts by mass or less, More preferably, the content is 30 parts by mass or more and 80 parts by mass or less, It is particularly preferable that the content is 40 parts by mass or more and 77 parts by mass or less, The most preferable range is 50 parts by mass or more and 75 parts by mass or less.

[0043] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the alicyclic epoxy compound is as follows: It is preferably 10 parts by mass or more and 80 parts by mass or less, More preferably, the content is 15 parts by mass or more and 75 parts by mass or less, More preferably, the content is 20 parts by mass or more and 70 parts by mass or less, It is particularly preferable that the content is 25 parts by mass or more and 65 parts by mass or less, It is particularly preferable that the amount is 30 parts by mass or more and 60 parts by mass or less. It is particularly preferable that the amount is 35 parts by mass or more and 55 parts by mass or less.

[0044] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the alicyclic epoxy compound in 100 parts by mass of the composition is It is preferably 1 part by mass or more and 30 parts by mass or less, More preferably, the content is 2 parts by mass or more and 20 parts by mass or less, More preferably, the content is 3 parts by mass or more and 15 parts by mass or less, It is particularly preferable that the amount is 5 parts by mass or more and 10 parts by mass or less.

[0045] (2) Aromatic epoxy compounds The aromatic epoxy compound refers to a compound having an aromatic ring and an epoxy group, but not having an alicyclic epoxy group. The aromatic epoxy compound may have a plurality of epoxy groups. Two or more of the aromatic epoxy compounds may be used in combination. The aromatic ring constituting the aromatic epoxy compound is not particularly limited as long as it is a ring having aromaticity, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, etc. In the present disclosure, the aromatic ring is preferably a benzene ring, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength.

[0046] Examples of such aromatic epoxy compounds include mono- and polyglycidyl ethers of monohydric phenols such as phenol, cresol, and butylphenol, or alkylene oxide adducts thereof; mono- and polyglycidyl ethers of polyhydric phenols having at least one aromatic ring, or alkylene oxide adducts thereof; glycidyl ethers or epoxy novolac resins of bisphenol A, bisphenol F, or compounds obtained by further adding alkylene oxides to these; mono- and polyglycidyl ethers of aromatic compounds having two or more phenolic hydroxyl groups, such as resorcinol, hydroquinone, and catechol; polyglycidyl ethers of aromatic compounds having two or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethanol, and benzenedibutanol; and phthalic acid. glycidyl esters of polybasic aromatic compounds having two or more carboxylic acids, such as terephthalic acid and trimellitic acid; glycidyl esters of benzoic acids, such as benzoic acid, toluic acid and naphthoic acid; epoxidized products of styrene oxide or divinylbenzene; condensation products of epichlorohydrin with trisphenol compounds, such as 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-4-[α,α-bis(4-hydroxyphenyl)ethyl]benzene, 1,3,5-tris[α-methyl-α-(4-hydroxyphenyl)ethyl]benzene, 1,1,1-tris(hydroxyphenyl)methane, 1-[α-methyl-α-(4-hydroxyphenyl)ethyl]-3-[α,α-bis(4-hydroxyphenyl)ethyl]benzene and 1,1,1-tris(4-hydroxyphenyl)ethane, and the like. Examples of the alkylene oxide used in the alkylene oxide adduct include ethylene oxide and propylene oxide.

[0047] In the present disclosure, from the viewpoint that the composition can easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, it is preferable that the aromatic epoxy compound contains an aromatic bifunctional epoxy compound or an aromatic polyfunctional epoxy compound.

[0048] (a) Aromatic difunctional epoxy compounds The aromatic bifunctional epoxy compound refers to an aromatic epoxy compound having two epoxy groups. In the present disclosure, from the viewpoint of facilitating the formation of a cured product from the composition that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, the aromatic bifunctional epoxy compound is preferably a compound represented by the following general formula (B-1):

[0049] [ka]

[0050] In general formula (B-1), R 101 each independently represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, r1 represents a number between 0 and 20, X 1 and X 2 each independently represents a divalent aromatic hydrocarbon group having an aromatic ring.

[0051] R in the above general formula (B-1) 101 Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (A-1) include R 1 In the alkyl group having 1 to 20 carbon atoms, such as those represented by the formula (I), groups having a predetermined number of carbon atoms are exemplified.

[0052] X in the above general formula (B-1) 1 and X 2 Examples of the divalent aromatic hydrocarbon group having an aromatic ring represented by the formula (I) include a group in which two hydrogen atoms have been removed from an aromatic ring, and a group in which an alkylene group is linked to a group in which two hydrogen atoms have been removed from an aromatic ring. In the present disclosure, from the viewpoint that the composition can easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, it is preferable that the aromatic ring in the divalent aromatic hydrocarbon group having an aromatic ring is a benzene ring.

[0053] Examples of the divalent aromatic hydrocarbon group having an aromatic ring include groups represented by the following formulae (B-2), (B-3) and (B-4). * in the formula represents X in the general formula (B-1) 1 or X 2 represents the bonding position of the oxygen atom linked to the

[0054] [ka]

[0055] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition temperature, and can easily form a cured product having excellent dimensional stability and adhesive strength, the aromatic bifunctional epoxy compound is preferably selected from the group consisting of X in the general formula (B-1) 1 or X 2 is more preferably a group represented by formula (B-2), and X 1 and X 2 is more preferably a group represented by formula (B-2).

[0056] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, In the general formula (B-1), r1 is preferably 0 or more and 10 or less, more preferably 0 or more and 5 or less, and even more preferably 0 or more and 3 or less.

[0057] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, R in the above general formula (B-1) 101 is more preferably a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 3 carbon atoms, even more preferably a hydrogen atom, a hydroxyl group, or a methyl group, particularly preferably a hydrogen atom or a hydroxyl group, and most preferably a hydroxyl group.

[0058] (b) Aromatic polyfunctional epoxy compounds The aromatic polyfunctional epoxy compound refers to an aromatic epoxy compound having three or more epoxy groups. In the present disclosure, the aromatic polyfunctional epoxy compound is preferably a compound represented by the following general formula (B-5), from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength.

[0059] [ka]

[0060] In general formula (B-5), R 102 , R 103 , R 104 , R 105 , R 106 , R 107 and R 108 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; X 3 represents a glycidyl ether group, or a divalent aliphatic hydrocarbon group which is unsubstituted or substituted with a hydroxyl group or an amino group, r2 represents 1 or 2; If r2 is 1, then X 3 is a glycidyl ether group, If r2 is 2, then X 3 is a divalent aliphatic hydrocarbon group which is unsubstituted or substituted with a hydroxyl group or an amino group.

[0061] X in the above general formula (B-5) 3Examples of the unsubstituted aliphatic hydrocarbon group in the divalent aliphatic hydrocarbon group which is unsubstituted or substituted with a hydroxyl group or an amino group, and which is represented by the following formula, include an alkylene group, an ether bond, a carbonyl group, a carbonate group, or a group obtained by combining these.

[0062] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, X 3 is preferably a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, which is substituted or unsubstituted with a hydroxyl group, It is more preferable that the divalent aliphatic hydrocarbon group has 2 to 8 carbon atoms and is substituted with a hydroxyl group. It is more preferably a divalent aliphatic hydrocarbon group having 2 to 5 carbon atoms and substituted with a hydroxyl group.

[0063] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The compound represented by the general formula (B-5) is Preferably, it is a mixture of a compound where r2=1 and a compound where r2=2, The content of the compound in which r2=1 in the mixture is more preferably 50% by mass or more, and further preferably 80% by mass or more.

[0064] As the aromatic epoxy compound, commercially available products can be used. Commercially available products of the aromatic bifunctional epoxy compounds include, for example, Denacol EX-201, Denacol EX-203, Denacol EX-711, and Denacol EX-721; ADEKA RESIN EP-4000, ADEKA RESIN EP-4005, ADEKA RESIN EP-4100, ADEKA RESIN EP-4100E, ADEKA RESIN EP-4100G, ADEKA RESIN EP-4300E, ADEKA RESIN EP-4400, ADEKA RESIN EP-4520S, ADEKA RESIN EP-4530, and ADEKA RESIN EP -4901, ADEKA RESIN EP-4901E (all manufactured by ADEKA Corporation); OGSOL PG-100, OGSOL EG-200, OGSOL EG-210, OGSOL EG-250 (all manufactured by Osaka Gas Chemicals Co., Ltd.); jER-1001, jER-1002, jER-1004, jER-1007, jER-1009, jER-1010, Epikote YX8800 (all manufactured by Mitsubishi Chemical Corporation); HP4032, HP4032D (all manufactured by DIC Corporation), and the like.

[0065] Commercially available examples of the aromatic polyfunctional epoxy compound include ADEKA RESIN EP-5100R (manufactured by ADEKA Corporation); TECHMORE VG-3101L (manufactured by Air Water Inc.), MARPROOF G-0105SA, and MARPROOF G-0130SP (all manufactured by NOF Corporation); EPICRON N-665, EPICRON HP-7200, and HP4700 (all manufactured by DIC Corporation); and EOCN-1020, EOCN-102S, EOCN-103S, EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, and NC-7000L (all manufactured by Nippon Kayaku Co., Ltd.).

[0066] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The molecular weight of the aromatic epoxy compound is Preferably, it is 100 or more and 1,300 or less, More preferably, it is 110 or more and 1,100 or less, It is more preferable that the molecular weight is 120 or more and 800 or less, It is particularly preferable that the molecular weight is 130 or more and 500 or less, It is most preferable that the ratio is 140 or more and 400 or less. In this specification, when the molecular weight is the average value of multiple compounds, it is referred to as the weight average molecular weight. The weight average molecular weight of the curable component is measured, for example, by GPC, and a calibration curve is created using standard polystyrene of known molecular weight (molecular weight distribution = 1). Based on this calibration curve, the weight average molecular weight is calculated from the GPC retention time.

[0067] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and is easy to form a cured product having excellent dimensional stability and adhesive strength, the epoxy equivalent of the aromatic epoxy compound is Preferably, it is 80 g / eq or more and 600 g / eq or less, More preferably, it is 120 g / eq or more and 550 g / eq or less, It is more preferable that the molecular weight is 140 g / eq or more and 500 g / eq or less, It is particularly preferable that the molecular weight is 150 g / eq or more and 480 g / eq or less.

[0068] In the present disclosure, when the composition contains the aromatic epoxy compound, the composition is excellent in deep curing, has a small cure shrinkage rate, and is easily able to form a cured product having a high glass transition point, dimensional stability, and adhesive strength, and from the viewpoint of: The content of the aromatic epoxy compound is as follows: It is preferably 1 part by mass or more and 80 parts by mass or less, More preferably, the content is 5 parts by mass or more and 70 parts by mass or less, More preferably, the content is 10 parts by mass or more and 65 parts by mass or less, It is particularly preferable that the content is 20 parts by mass or more and 60 parts by mass or less, The most preferred range is 25 parts by mass or more and 55 parts by mass or less.

[0069] In the present disclosure, when the composition contains the aromatic epoxy compound, the composition is able to easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength. From this viewpoint, when the composition contains the aromatic epoxy compound, The content of the aromatic epoxy compound is as follows: It is preferably 10 parts by mass or more and 80 parts by mass or less, More preferably, the content is 10 parts by mass or more and 75 parts by mass or less, More preferably, the content is 10 parts by mass or more and 70 parts by mass or less, It is particularly preferable that the content is 10 parts by mass or more and 65 parts by mass or less, It is particularly preferable that the amount is 10 parts by mass or more and 60 parts by mass or less.

[0070] In the present disclosure, when the composition contains the aromatic epoxy compound, the composition is excellent in deep curing, has a small cure shrinkage rate, and is easily able to form a cured product having a high glass transition point, dimensional stability, and adhesive strength, and from the viewpoint of: The content of the aromatic epoxy compound in 100 parts by mass of the composition is It is preferably 1.0 part by mass or more and 30 parts by mass or less, More preferably, the content is 1.5 parts by mass or more and 20 parts by mass or less, More preferably, the content is 1.8 parts by mass or more and 15 parts by mass or less, It is particularly preferable that the amount is 2 parts by mass or more and 12 parts by mass or less.

[0071] (3) Aliphatic epoxy compounds The aliphatic epoxy compound refers to a compound having an epoxy group but not having an aromatic ring or an alicyclic epoxy group. The aliphatic epoxy compound may have multiple epoxy groups. Two or more of the aliphatic epoxy compounds may be used in combination.

[0072] Examples of such aliphatic epoxy compounds include aliphatic ring-containing epoxy compounds and chain aliphatic epoxy compounds.

[0073] (a) Aliphatic ring-containing epoxy compound The aliphatic ring-containing epoxy compound refers to an aliphatic epoxy compound containing an aliphatic ring such as an aliphatic hydrocarbon ring or an aliphatic heterocycle.

[0074] The aliphatic hydrocarbon ring may be any ring-forming ring in which the only ring-forming atoms are carbon atoms and the ring does not have aromaticity. In addition, the aliphatic hydrocarbon ring may have one or more hydrogen atoms substituted with a linear or branched alkyl group. Examples of such aliphatic hydrocarbon rings include monocyclic aliphatic hydrocarbon rings such as a cyclohexane ring; structures in which multiple monocyclic aliphatic hydrocarbon rings such as bicyclohexyl are directly bonded via a carbon-carbon single bond, an alkylene group having from 1 to 4 carbon atoms, an ether bond, a thioether bond, a carbonyl group, an ester bond, or a divalent group formed by a combination of these groups; and polycyclic aliphatic hydrocarbon rings in which two or more monocyclic aliphatic hydrocarbon rings such as an isobornyl ring, an adamantane ring, a dicyclopentene ring, a dicyclopentane ring, a tricyclodecane ring, a norbornene ring, or a norbornane ring share one or more carbon atoms in the ring.

[0075] The aliphatic heterocycle may be any ring-forming atom that contains atoms other than carbon atoms and does not have aromaticity, and examples thereof include a pyrrolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a thiomorpholine ring, a homopiperidine ring, a homopiperazine ring, a tetrahydropyridine ring, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, a tetrahydrofuran ring, a tetrahydropyran ring, a dihydrobenzofuran ring, a tetrahydrocarbazole ring, a caprolactam ring, an isocyanuric ring, and a hydantoin ring.

[0076] Examples of the aliphatic ring-containing epoxy compound include compounds represented by the following general formula (C-1) or (C-2).

[0077] [ka]

[0078] In general formula (C-1), X 4 represents a group in which two hydrogen atoms have been removed from an aliphatic ring, and one or more of the hydrogen atoms in the aliphatic ring may be substituted with a linear or branched alkyl group having 1 to 10 carbon atoms. In the general formula (C-1), X 4 Examples of the group represented by the formula (I) in which two hydrogen atoms have been removed from an aliphatic ring include groups in which two hydrogen atoms have been removed from the above-mentioned aliphatic hydrocarbon ring or aliphatic heterocycle.

[0079] [ka]

[0080] In general formula (C-2), R 111 represents an alkyl group having 1 to 10 carbon atoms, r3 represents an integer between 1 and 30.

[0081] R in the above general formula (C-2) 111 Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (A-1) include R 1 In the alkyl group having 1 to 20 carbon atoms, such as those represented by the formula (I), groups having a predetermined number of carbon atoms are exemplified.

[0082] (b) Acyclic aliphatic epoxy compounds The chain aliphatic epoxy compound refers to an aliphatic epoxy compound that does not contain an aliphatic ring. Examples of the chain aliphatic epoxy compound include compounds described in JP-A-2005-99735.

[0083] In the present disclosure, from the viewpoint that the composition can easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, it is preferable that the aliphatic epoxy compound includes an aliphatic ring-containing epoxy compound.

[0084] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The epoxy equivalent of the aliphatic epoxy compound Preferably, it is 80 g / eq or more and 400 g / eq or less, It is more preferable that the content is 120 g / eq or more and 300 g / eq or less, It is more preferable that the molecular weight is 140 g / eq or more and 250 g / eq or less, It is particularly preferable that the molecular weight is 160 g / eq or more and 200 g / eq or less.

[0085] In the present disclosure, when the composition contains the aliphatic epoxy compound, the composition is excellent in deep curing, has a small cure shrinkage rate, and is easily able to form a cured product having a high glass transition point, dimensional stability, and adhesive strength, and from the viewpoint of: The content of the aliphatic epoxy compound is as follows: It is preferably 1 part by mass or more and 80 parts by mass or less, More preferably, the content is 5 parts by mass or more and 70 parts by mass or less, More preferably, the content is 10 parts by mass or more and 65 parts by mass or less, It is particularly preferable that the content is 20 parts by mass or more and 60 parts by mass or less, The most preferred range is 25 parts by mass or more and 55 parts by mass or less.

[0086] In the present disclosure, when the composition contains the aliphatic epoxy compound, the composition is excellent in deep curing, has a small cure shrinkage rate, and is easily able to form a cured product having a high glass transition point, dimensional stability, and adhesive strength, and from the viewpoint of: The content of the aliphatic epoxy compound is as follows: It is preferably 1 part by mass or more and 80 parts by mass or less, More preferably, the content is 5 parts by mass or more and 60 parts by mass or less, More preferably, the content is 8 parts by mass or more and 40 parts by mass or less, It is particularly preferable that the amount is 10 parts by mass or more and 30 parts by mass or less.

[0087] In the present disclosure, when the composition contains the aliphatic epoxy compound, the composition is excellent in deep curing, has a small cure shrinkage rate, and is easily able to form a cured product having a high glass transition point, dimensional stability, and adhesive strength, and from the viewpoint of: The content of the aliphatic epoxy compound in 100 parts by mass of the composition is It is preferably 0.5 parts by mass or more and 30 parts by mass or less, More preferably, the content is 1.0 part by mass or more and 20 parts by mass or less, More preferably, the content is 1.5 parts by mass or more and 10 parts by mass or less, It is particularly preferable that the content be 2.0 parts by mass or more and 5 parts by mass or less.

[0088] The composition may contain both an aromatic epoxy compound and an aliphatic epoxy compound. However, from the viewpoint of facilitating the formation of a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, it is preferable that the composition contain either an aromatic epoxy compound or an aliphatic epoxy compound.

[0089] (4) Oxetane compounds The oxetane compound refers to a compound having an oxetanyl group but not having an epoxy group or an alicyclic epoxy group. The oxetane compound may have multiple oxetanyl groups in one molecule. Two or more types of the oxetane compounds may be combined.

[0090] Examples of such oxetane compounds include aromatic oxetane compounds and aliphatic oxetane compounds.

[0091] (a) Aromatic oxetane compounds The aromatic oxetane compound refers to an oxetane compound containing an aromatic ring. The aromatic ring is the same as the aromatic ring described in the section "A2. Aromatic Epoxy Compounds." In the present disclosure, the aromatic ring is preferably a benzene ring, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, dimensional stability, and excellent adhesive strength. Examples of the aromatic oxetane compound include compounds represented by the following general formula (D-1).

[0092] [ka]

[0093] In general formula (D-1), X 5 represents an aromatic ring group having 6 to 20 carbon atoms, R 121 represents an alkyl group having 1 to 10 carbon atoms, r4 represents a number between 1 and 5 inclusive.

[0094] X in the above general formula (D-1) 5 The aromatic ring group having 6 to 20 carbon atoms represented by the formula: It represents a group in which a total of r4 hydrogen atoms have been removed from one or more aromatic rings. Examples of "a group in which a total of r4 hydrogen atoms have been removed from multiple aromatic rings" include groups in which a total of r4 hydrogen atoms have been removed from multiple aromatic rings linked via direct bonds or linking groups. Examples of linking groups include -S-, -O-, a carbonyl group, an alkylene group having 1 to 4 carbon atoms, and groups formed by combinations thereof. In the aromatic ring group, a hydrogen atom on the aromatic ring may be substituted with an alkyl group having 1 to 5 carbon atoms.

[0095] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The aromatic ring group preferably has 6 to 15 carbon atoms, is more preferably a group in which r4 hydrogen atoms have been removed from a benzene ring or biphenyl, and is particularly preferably a group in which r4 hydrogen atoms have been removed from biphenyl.

[0096] R in the above general formula (D-1) 121 Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (A-1) include R 1 In the alkyl group having 1 to 20 carbon atoms, groups having a predetermined number of carbon atoms such as:

[0097] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, Above R 121 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and particularly preferably an ethyl group.

[0098] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The above r4 is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and particularly preferably 2.

[0099] In the present disclosure, when the composition contains the aromatic oxetane compound, it becomes easy to form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from this viewpoint, The content of the aromatic oxetane compound is as follows: It is preferably 30 parts by mass or more, More preferably, it is 40 parts by mass or more, More preferably, the content is 40 parts by mass or more and 90 parts by mass or less, It is particularly preferable that the amount is 50 parts by mass or more and 85 parts by mass or less.

[0100] In the present disclosure, when the composition contains the aromatic oxetane compound, it becomes easy to form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from this viewpoint, The content of the aromatic oxetane compound is as follows: It is preferably 5 parts by mass or more and 80 parts by mass or less, More preferably, the content is 10 parts by mass or more and 50 parts by mass or less, More preferably, the content is 15 parts by mass or more and 50 parts by mass or less, It is particularly preferable that the amount is 20 parts by mass or more and 40 parts by mass or less.

[0101] In the present disclosure, when the composition contains the aromatic oxetane compound, it becomes easy to form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from this viewpoint, The content of the aromatic oxetane compound in 100 parts by mass of the composition is It is preferably 0.5 parts by mass or more and 30 parts by mass or less, More preferably, the content is 1 part by mass or more and 15 parts by mass or less, More preferably, the content is 1.5 parts by mass or more and 10 parts by mass or less, It is particularly preferable that the amount is 2 parts by mass or more and 8 parts by mass or less.

[0102] (b) Aliphatic oxetane compounds The aliphatic oxetane compound refers to an oxetane compound that does not contain an aromatic ring. Examples of the aliphatic oxetane compound include compounds represented by the following general formula (D-2).

[0103] [ka] (In general formula (D-2), X 6 represents an oxygen atom, a hydroxyl group, a silyl ether group, or an r pentavalent aliphatic hydrocarbon group having from 1 to 10 carbon atoms which may have an oxygen atom; R 122 represents an alkyl group having 1 to 10 carbon atoms, r5 represents a number from 1 to 10.

[0104] R in the above general formula (D-2) 122 Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (A-1) include R 1 In the alkyl group having 1 to 20 carbon atoms, groups having a predetermined number of carbon atoms such as:

[0105] X in formula (D-2) 6 Examples of the silyl ether group used in the above include groups represented by the following formula (ds):

[0106] [ka] (R m represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, g and h each represent a number of 0 to 2 satisfying the relationship g+h=2, and k represents a number of 1 to 4. * represents a bond.

[0107] X in the above general formula (D-2) 6 The r pentavalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and optionally containing an oxygen atom, represented by the formula (I), may be linear or branched, some of the hydrogen atoms in the aliphatic hydrocarbon group may be substituted with hydroxyl groups, amino groups, etc., and methylene groups in the aliphatic hydrocarbon group may be substituted with an ether bond, a thioether group, a silyl ether group (for example, -OSiR a R b -, R a and Rb is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) It may be substituted with a carbonyl group, an ester group, or a divalent group formed by combining these groups. Examples of the r5-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms and optionally having an oxygen atom include, for example, when r5 is 1, an alkyl group having 1 to 10 carbon atoms. When r5 is 2 or more, examples include groups in which r5-1 hydrogen atoms have been removed from the above alkyl groups. Examples of the alkyl group having 1 to 10 carbon atoms include R in the general formula (A-1) described in the section "(1) Alicyclic epoxy compound" in "A1. Curable compound." 1 In the alkyl group having 1 to 20 carbon atoms, such as those represented by the formula (I), groups having a predetermined number of carbon atoms are exemplified.

[0108] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and can easily form a cured product having excellent dimensional stability and adhesive strength, X 5 More preferably, is an oxygen atom or a silyl ether group.

[0109] In the present disclosure, from the viewpoint that the composition can easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, r5 in the general formula (D-2) above is preferably a number of 1 or more and 3 or less, more preferably a number of 1 or more and 2 or less, and particularly preferably 2.

[0110] When r5 is 2, the composition has excellent deep curing properties, a small cure shrinkage rate, and is easy to form a cured product having a high glass transition point, dimensional stability, and adhesive strength. From this viewpoint, X in general formula (D-2) 6 is an oxygen atom, and R 122 is preferably an alkyl group having 1 to 6 carbon atoms, X 6 is an oxygen atom, and R 122 is more preferably an alkyl group having 2 to 4 carbon atoms, X 6 is an oxygen atom, and R 122 However, alkyl groups having 2 or 3 carbon atoms are particularly preferred.

[0111] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The molecular weight of the aliphatic oxetane compound is Preferably, it is 100 or more and 3,000 or less, More preferably, it is 130 or more and 2,000 or less, More preferably, it is 150 or more and 1,800 or less, It is particularly preferable that the molecular weight is 180 or more and 1,600 or less.

[0112] In the present disclosure, when the composition contains the aliphatic oxetane compound, it becomes easy to form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from this viewpoint, The content of the aliphatic oxetane compound is as follows: It is preferably 5 parts by mass or more, More preferably, it is 10 parts by mass or more, More preferably, the content is 20 parts by mass or more and 100 parts by mass or less, It is particularly preferable that the amount is 25 parts by mass or more and 50 parts by mass or less.

[0113] In the present disclosure, when the composition contains the aliphatic oxetane compound, it becomes easy to form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from this viewpoint, The content of the aliphatic oxetane compound is as follows: It is preferably 1 part by mass or more and 50 parts by mass or less, More preferably, the content is 3 parts by mass or more and 30 parts by mass or less, More preferably, the content is 5 parts by mass or more and 25 parts by mass or less, It is particularly preferable that the amount is 8 parts by mass or more and 20 parts by mass or less.

[0114] In the present disclosure, when the composition contains the aliphatic oxetane compound, it becomes easy to form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from this viewpoint, The content of the aliphatic oxetane compound in 100 parts by mass of the composition is It is preferably 0.5 parts by mass or more and 30 parts by mass or less, More preferably, the content is 1 part by mass or more and 15 parts by mass or less, More preferably, the content is 1.5 parts by mass or more and 10 parts by mass or less, It is particularly preferable that the amount is 2 parts by mass or more and 8 parts by mass or less.

[0115] In the present disclosure, when the composition contains the aliphatic oxetane compound and the aromatic oxetane compound, the composition is able to easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, and an excellent balance between a high glass transition point, dimensional stability, and adhesive strength, and from this viewpoint, The content of the aliphatic oxetane compound is, relative to 100 parts by mass of the aromatic oxetane compound, Preferably, the content is 5 parts by mass or more and 350 parts by mass or less, More preferably, the content is 10 parts by mass or more and 250 parts by mass or less, More preferably, the content is 20 parts by mass or more and 200 parts by mass or less, It is particularly preferable that the content is 40 parts by mass or more and 130 parts by mass or less.

[0116] (c) Oxetane compounds In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, the oxetane compound preferably includes an aromatic oxetane compound, and more preferably includes a combination of an aromatic oxetane compound and an aliphatic oxetane compound.

[0117] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The molecular weight of the oxetane compound is Preferably, it is 100 or more and 1,000 or less, More preferably, it is 150 or more and 600 or less, It is more preferable that the molecular weight is 180 or more and 500 or less, It is particularly preferable that the molecular weight is 190 or more and 420 or less.

[0118] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the oxetane compound is as follows: It is preferably 5 parts by mass or more and 80 parts by mass or less, More preferably, the content is 10 parts by mass or more and 65 parts by mass or less, More preferably, the content is 15 parts by mass or more and 60 parts by mass or less, It is particularly preferable that the amount is 20 parts by mass or more and 50 parts by mass or less.

[0119] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the oxetane compound in 100 parts by mass of the composition is It is preferably 0.5 parts by mass or more and 30 parts by mass or less, More preferably, the content is 1 part by mass or more and 20 parts by mass or less, More preferably, the content is 1.5 parts by mass or more and 15 parts by mass or less, It is particularly preferable that the amount is 3 parts by mass or more and 10 parts by mass or less.

[0120] A2. Polymerization initiator In the present disclosure, the polymerization initiator includes a sulfonium salt-type cationic photopolymerization initiator and an iodonium salt-type cationic photopolymerization initiator.

[0121] (1) Sulfonium salt-type photocationic polymerization initiator The sulfonium salt-type photocationic polymerization initiator has a structure of a sulfonium cation having at least one sulfonio group and an anion, and can be used without particular limitation as long as it can release a substance (acid) that initiates cationic polymerization upon light irradiation. Two or more of the sulfonium salt-type photocationic polymerization initiators may be used in combination.

[0122] Examples of the sulfonium cation include the cations described in Group I and Group II below, but the present invention is not limited to these structures.

[0123] [ka]

[0124] [ka]

[0125] The anion is a counter ion (anion) of an acid generated by irradiating a sulfonium salt-type cationic photopolymerization initiator with active energy rays (visible light, ultraviolet light, electron beams, X-rays, etc.), and is, for example, M(Y) a - , RfSO3 - , (RfSO2)3C - , (RfSO2)2N - , (Rf) b PF 6-b - , (Rx) c BY 4-c - etc.

[0126] M represents a phosphorus atom, a boron atom, an arsenic atom, or an antimony atom; Y represents a halogen atom; Rf represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom; Rx represents a phenyl group or a phenyl group in which at least one hydrogen atom is substituted with a halogen atom, a trifluoromethyl group, a nitro group, or a cyano group; a represents an integer between 4 and 6, b represents an integer of 1 or more and 5 or less, c represents an integer of 1 or more and 4 or less.

[0127] M(Y)a - As an anion represented by the formula, for example, AsF6 - , SbF6 - , PF6 - , BF4 - etc.

[0128] RfSO3 - Examples of anions represented by the formula include CF3SO3 - , CF3CF2SO3 - , (CF3)2CFSO3 - , CF3CF2CF2SO3 - , (CF3)2CFCF2SO3 - , CF3CF2(CF3)CFSO3 - , (CF3)3CSO3 - , CF3CF2CF2CF2SO3 - etc.

[0129] (RfSO2)3C - Examples of the anion represented by the formula include (CF3SO2)3C - , (CF3CF2SO2)3C - , ((CF3)2CFSO2)3C - , (CF3CF2CF2SO2)3C - , ((CF3)2CFCF2SO2)3C - , (CF3CF2(CF3)CFSO2)3C - , ((CF3)3CSO2)3C - etc.

[0130] (RfSO2)2N - Examples of the anion represented by the formula include (CF3SO2)2N - , (CF3CF2SO2)2N - , ((CF3)2CFSO2)2N - , (CF3CF2CF2SO2)2N - , ((CF3)2CFCF2SO2)2N - , (CF3CF2(CF3)CFSO2)2N - , ((CF3)2CFCF2SO2)2N - , (CF3CF2(CF3)CFSO2)2N - , ((CF3)3CSO2)2N - etc.

[0131] (Rf) b PF 6-b - Examples of the anion represented by the formula include (CF3CF2)2PF4 - , (CF3CF2)3PF3 - , ((CF3)2CF)2PF4 - , ((CF3)2CF)3PF3 - , (CF3CF2CF2)2PF4 - , (CF3CF2CF2)3PF3 - , ((CF3)2CFCF2)2PF4 - , ((CF3)2CFCF2)3PF3 - , (CF3CF2CF2CF2)2PF4 - or (CF3CF2CF2CF2)3PF3 - Examples of the anion include anions represented by the following formula:

[0132] (Rx) c BY 4-c - Examples of the anion represented by the formula include (C6F5)4B - , ((CF3)2C6H3)4B - , (CF3C6H4)4B - , (C6F5)2BF2 - , C6F5BF3 - or (C6H3F2)4B- Examples of the anion include anions represented by the following formula:

[0133] In the present disclosure, the anion is selected from the group consisting of BF4, BF5, BF6, BF7, BF8, BF9, BF10, BF11, BF12, BF13, BF14, BF15, BF16, BF17, BF18, BF19, BF20, BF21, BF22, BF23, BF24, BF25, BF30, BF4 - , B(C6F5)4 - , SbF6 - , SbCl6 - , SbF4 - , FSO3 - , AsF6 - , PF6 - , CF3SO3 - , CF3(CF2)3SO3 - , (CF3SO2)3C - , (CF3SO2)2N - Preferably, B(C6F5)4 - , SbF6 - , SbCl6 - , SbF4 - , FSO3 - , AsF6 - , PF6 - , CF3SO3 - , CF3(CF2)3SO3 - , C(CF3SO2)3 - More preferably, B(C6F5)4 - , SbF6 - , SbCl6 - , SbF4 - , FSO3 - , AsF6 - , PF6 - , CF3SO3 - , CF3(CF2)3SO3 - , (CF3SO2)3C - More preferably, B(C6F5)4 - , SbF6 - , PF6 - , CF3SO3 - , CF3(CF2)3SO3 - , (CF3SO2)3C -It is particularly preferred that B(C6F5)4 - It is most preferred that:

[0134] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, the anion is preferably an anion containing a boron atom, and (Rx) c BY 4-c - More preferably, (C6F5)4B - , ((CF3)2C6H3)4B - , (CF3C6H4)4B - , (C6F5)2BF2 - , C6F5BF3 - or (C6H3F2)4B - More preferably, (C6F5)4B - It is particularly preferred that:

[0135] Examples of the sulfonium salt-type photocationic polymerization initiator include: Triphenylsulfonium tetrafluoroborate, triphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris(trifluoromethylsulfonyl)methanide, triphenylsulfonium bis(trifluoromethylsulfonyl)amide, diphenyl-4-methylphenylsulfonium tetrafluoroborate, diphenyl-4-methylphenylsulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl-4-methylphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methylphenylsulfonium hexafluoroantimonate, diphenyl-4-methylphenylsulfonium hexafluorophosphate, diphenyl Diphenyl-4-methylphenylsulfonium tris(trifluoromethylsulfonyl)methanide, diphenyl-4-methylphenylsulfonium bis(trifluoromethylsulfonyl)amide, triphenyl-p-tolylsulfonium tetrafluoroborate, triphenyl-p-tolylsulfonium tris(pentafluoroethyl)trifluorophosphate, triphenyl-p-tolylsulfonium tetrakis(pentafluorophenyl)borate, triphenyl-p-tolylsulfonium trifluoromethanesulfonate, triphenyl-p-tolylsulfonium hexafluoroantimonide triphenylsulfonium hexafluorophosphate, triphenylsulfonium tris(trifluoromethylsulfonyl)methanide, triphenylsulfonium bis(trifluoromethylsulfonyl)amide, diphenyl((4-phenylthio)phenyl)sulfonium tetrafluoroborate, diphenyl((4-phenylthio)phenyl)sulfonium tris(pentafluoroethyl)trifluorophosphate, diphenyl((4-phenylthio)phenyl)sulfonium tetrakis(pentafluorophenyl)borate,Diphenyl((4-phenylthio)phenyl)sulfonium trifluoromethanesulfonate, diphenyl((4-phenylthio)phenyl)sulfonium hexafluoroantimonate, diphenyl((4-phenylthio)phenyl)sulfonium hexafluorophosphate, diphenyl((4-phenylthio)phenyl)sulfonium tris(trifluoromethylsulfonyl)methanide, diphenyl((4-phenylthio)phenyl)sulfonium bis(trifluoromethylsulfonyl)amide, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium tetrafluoroborate, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium tris(pentafluoroethyl)trifluorophosphate, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium tetrakis(pentafluorophenyl)borate, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium trifluoromethanesulfonate, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium hexafluorophosphate Fluoroantimonate, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium hexafluorophosphate, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium tris(trifluoromethylsulfonyl)methanide, (4-benzoylphenyl)bis(4-fluorophenyl)sulfonium bis(trifluoromethylsulfonyl)amide, (4-phenoxyphenyl)diphenylsulfonium tetrafluoroborate, (4-phenoxyphenyl)diphenylsulfonium tetrakis Examples of the diphenylsulfonium bis(trifluoromethylsulfonyl)amide include (4-phenoxyphenyl)diphenylsulfonium tris(pentafluorophenyl)borate, (4-phenoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, (4-phenoxyphenyl)diphenylsulfonium hexafluoroantimonate, (4-phenoxyphenyl)diphenylsulfonium hexafluorophosphate, (4-phenoxyphenyl)diphenylsulfonium tris(trifluoromethylsulfonyl)methanide, and (4-phenoxyphenyl)diphenylsulfonium bis(trifluoromethylsulfonyl)amide.

[0136] Commercially available sulfonium salt-type photocationic polymerization initiators include, for example, TS-01, TS-91 (manufactured by Sanwa Chemical Co., Ltd.), CPI-100P, CPI-101A, CPI-200K, CPI-100B, CPI-310B, CPI-310FG, VC-1S, VC-1FG, CPI-410S, CPI-410B, and ES-1B (manufactured by San-Apro Co., Ltd.); WPAG-336, WPAG-367, WPAG-370, and WP Examples include AG-469 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), TR-PAG-201 / 201S, TR-PAG-202 / 202S, TR-PAG-20101, TR-PAG-20108 (manufactured by TRONLY); UVI-6992, UVI-6976 (manufactured by The Dow Chemical Company); ADEKA ARCLES SP-170, ADEKA ARCLES SP-292, ADEKA ARCLES SP-295 (manufactured by ADEKA Corporation), and Ominicat 270 (manufactured by IGM Resins BV).

[0137] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the sulfonium salt-type photocationic polymerization initiator is, in 100 parts by mass of the polymerization initiator, It is preferably 80 parts by mass or less, More preferably, the content is 5 parts by mass or more and 70 parts by mass or less, More preferably, the content is 10 parts by mass or more and 60 parts by mass or less, It is particularly preferable that the amount is 15 parts by mass or more and 50 parts by mass or less. The content of the sulfonium salt-type photocationic polymerization initiator is, in 100 parts by mass of the cationic polymerization initiator, It is preferably 80 parts by mass or less, More preferably, the content is 5 parts by mass or more and 70 parts by mass or less, More preferably, the content is 10 parts by mass or more and 60 parts by mass or less, It is particularly preferable that the amount is 15 parts by mass or more and 50 parts by mass or less.

[0138] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the sulfonium salt-type photocationic polymerization initiator is, relative to 100 parts by mass of the curable component, It is preferably 0.05 parts by mass or more and 20 parts by mass or less, More preferably, the amount is 0.1 parts by mass or more and 10 parts by mass or less, More preferably, the content is 0.1 to 8 parts by mass, It is particularly preferable that the content be 0.5 parts by mass or more and 5 parts by mass or less.

[0139] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the sulfonium salt-type photocationic polymerization initiator in 100 parts by mass of the composition is It is preferably 5 parts by mass or less, More preferably, the content is 0.01 parts by mass or more and 3 parts by mass or less, More preferably, the content is 0.05 parts by mass or more and 1.5 parts by mass or less, It is particularly preferable that the amount is 0.1 part by mass or more and 1 part by mass or less.

[0140] (2) Iodonium salt-type photocationic polymerization initiator The iodonium salt-type photocationic polymerization initiator may be any compound known as a photocationic polymerization initiator, and examples thereof include compounds represented by the following general formula (E-1).

[0141] [ka]

[0142] In the above general formula (E-1), R 131 and R 132each independently represents a halogen atom, an alkyl group having from 1 to 10 carbon atoms, or an alkoxy group having from 1 to 10 carbon atoms, An - represents the cation moiety and the corresponding monovalent counter anion, r7 represents an integer between 0 and 5, r8 represents an integer between 0 and 5, If r7 or r8 is 2 or more, multiple R 131 or R 132 may be different groups.

[0143] R in the above general formula (E-1) 131 or R 132 Examples of the halogen atom represented by the formula (A-1) include R 1 The halogen atoms represented by the formula (I) and (II) are the same as those represented by the formula (I).

[0144] R in the above general formula (E-1) 131 or R 132 Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (A-1) include R 1 Examples of alkyl groups having 1 to 20 carbon atoms, such as those represented by the above formulae, include groups having a predetermined number of carbon atoms. In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, R in the above general formula (E-1) 131 or R 132 However, each independently, It is preferably an alkyl group having 1 to 5 carbon atoms, It is more preferable that the alkyl group has 1 to 4 carbon atoms. More preferably, it is an alkyl group having 1 to 3 carbon atoms.

[0145] R in the above general formula (E-1) 131 or R132 The alkoxy group having 1 to 10 carbon atoms represented by the formula (A-1) in "A1. Alicyclic epoxy compounds" above includes R 1 Examples of alkoxy groups having 1 to 12 carbon atoms, such as those represented by the formula (I), include groups having a specific number of carbon atoms. The same groups are mentioned.

[0146] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and is easy to form a cured product having excellent dimensional stability and adhesive strength, it is preferable that r7 and r8 in the general formula (E-1) are integers of 1 or more and 3 or less. It is more preferable that it is an integer of 1 or more and 2 or less. It is more preferably 1.

[0147] An in the above general formula (E-1) - The monovalent anion corresponding to the cation moiety represented by the formula (I) can be the same group as the anion described in the above section "(1) Sulfonium salt-type cationic photopolymerization initiator." In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and can easily form a cured product having excellent dimensional stability and adhesive strength, it is preferable to use an alkyl group represented by the general formula (An in (E-1)). - But (RfSO2)3C - or (Rx) c BY 4-c - It is preferred that (CF3SO2)3C - , (C6F5)4B - It is more preferable that: The definitions of Rf, Rx, Y, and c are the same as those described in the section "(1) Sulfonium salt-type photocationic polymerization initiator" in "A2. Polymerization initiator" above.

[0148] Examples of the compound represented by the general formula (E-1) include 4-isobutylphenyl-4'-methylphenyliodonium tetrafluoroborate, 4-isobutylphenyl-4'-methylphenyliodonium tetrakis(pentafluorophenyl)borate, 4-isobutylphenyl-4'-methylphenyliodonium trifluoromethanesulfonate, 4-isobutylphenyl-4'-methylphenyliodonium hexafluoroantimonate, and 4-isobutylphenyl-4'-methylphenyliodonium hexafluorophosphine. Phosphate, 4-isobutylphenyl-4'-methylphenyliodonium tris(trifluoromethylsulfonyl)methanide, 4-isobutylphenyl-4'-methylphenyliodonium bis(trifluoromethylsulfonyl)amide, Bis(dodecylphenyl)iodonium tetrafluoroborate, Bis(dodecylphenyl)iodonium trifluoromethanesulfonate, Bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, Bis(dodecylphenyl)iodonium trifluoromethanesulfonate Phosphonate, Bis(dodecylphenyl)iodonium hexafluoroantimonate, Bis(dodecylphenyl)iodonium hexafluorophosphate, Bis(dodecylphenyl)iodonium tris[fluorotris(trifluoromethylsulfonyl)]methanide, Bis(dodecylphenyl)iodonium bis(trifluoromethylsulfonyl)amide, 4-Isopropylphenyl-4'-methylphenyliodonium tetrafluoroborate, 4-Isopropylphenyl-4'-methylphenyliodonium trifluoromethane sulfonate, 4-isopropylphenyl-4'-methylphenyliodonium tetrakis(pentafluorophenyl)borate, 4-isopropylphenyl-4'-methylphenyliodonium trifluoromethanesulfonate, 4-isopropylphenyl-4'-methylphenyliodonium hexafluoroantimonate, 4-isopropylphenyl-4'-methylphenyliodonium hexafluorophosphate, 4-isopropylphenyl-4'-methylphenyliodonium tris(trifluoromethylsulfonyl)methanide,Examples of the iodonium bis(trifluoromethylsulfonyl)amide include 4-isopropylphenyl-4'-methylphenyliodonium bis(trifluoromethylsulfonyl)amide, bis(4-tertbutylphenyl)iodonium tetrafluoroborate, bis(4-tertbutylphenyl)iodonium trifluoromethanesulfonate, bis(4-tertbutylphenyl)iodonium tetrakis(pentafluorophenyl)borate, bis(4-tertbutylphenyl)iodonium trifluoromethanesulfonate, bis(4-tertbutylphenyl)iodonium hexafluoroantimonate, bis(4-tertbutylphenyl)iodonium hexafluorophosphate, bis(4-tertbutylphenyl)iodonium tris(trifluoromethylsulfonyl)methanide, and bis(4-tertbutylphenyl)iodonium bis(trifluoromethylsulfonyl)amide.

[0149] Commercially available organic iodonium salts represented by the general formula (E-1) include, for example, Omnicat 250 (manufactured by IGM Resins BV), DPI-105, MPI-103, MPI-105, BBI-101, BBI-102, BBI-103, and BBI-105 (all manufactured by Midori Chemical Co., Ltd.), PI2074 (manufactured by Solvay), and TR-PAG-30101, TR-PAG-30201, TR-PAG-30401, and TR-PAG-30408 ​​(manufactured by Dongguan GKEY Trading Co., Ltd.).

[0150] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the iodonium salt-type photocationic polymerization initiator is, in 100 parts by mass of the polymerization initiator, It is preferably 10 parts by mass or more, More preferably, the content is 10 parts by mass or more and 95 parts by mass or less, More preferably, 20 parts by mass or more and 85 parts by mass or less, It is particularly preferable that the content is 25 parts by mass or more and 80 parts by mass or less, It is particularly preferable that the amount is 30 parts by mass or more and 75 parts by mass or less. The content of the iodonium salt-type photocationic polymerization initiator is, in 100 parts by mass of the cationic polymerization initiator, It is preferably 30 parts by mass or more, More preferably, the content is 40 parts by mass or more and 95 parts by mass or less, More preferably, 45 parts by mass or more and 85 parts by mass or less, It is particularly preferable that the content is 50 parts by mass or more and 80 parts by mass or less, It is particularly preferable that the amount is 55 parts by mass or more and 75 parts by mass or less.

[0151] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the iodonium salt-type photocationic polymerization initiator is, relative to 100 parts by mass of the curable component, It is preferably 20 parts by mass or less, More preferably, it is 10 parts by mass or less, More preferably, the content is 1 to 5 parts by mass, It is particularly preferable that the content be 1.5 parts by mass or more and 4 parts by mass or less.

[0152] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the iodonium salt-type photocationic polymerization initiator in 100 parts by mass of the composition is It is preferably 5 parts by mass or less, More preferably, the content is 0.01 parts by mass or more and 3 parts by mass or less, More preferably, the content is 0.05 parts by mass or more and 1.5 parts by mass or less, It is particularly preferable that the content is 0.1 parts by mass or more and 1.3 parts by mass or less, It is particularly preferable that the amount is 0.3 to 1.0 parts by mass.

[0153] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the sulfonium salt-type photocationic polymerization initiator relative to 100 parts by mass of the iodonium salt-type photocationic polymerization initiator is It is preferably 1 part by mass or less, More preferably, the content is 3 parts by mass or more and 400 parts by mass or less, More preferably, the content is 5 parts by mass or more and 250 parts by mass or less, It is particularly preferable that the content is 10 parts by mass or more and 200 parts by mass or less, It is particularly preferable that the amount is 20 parts by mass or more and 120 parts by mass or less.

[0154] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and is easy to form a cured product having excellent dimensional stability and adhesive strength, it is preferable that the sulfonium salt-type photocationic polymerization initiator and the iodonium salt-type photocationic initiator have an anion containing a boron atom, and the (RfSO2)3C - or above (Rx) c BY 4-c - More preferably, (CF3SO2)3C - , (C6F5)4B - It is more preferred that (C6F5)4B - It is particularly preferred that

[0155] The sulfonium salt-type photocationic polymerization initiator and the iodonium salt-type photocationic initiator may have the same or different anions.

[0156] (3) Other polymerization initiators The composition may contain other polymerization initiators in addition to the sulfonium salt-type cationic photopolymerization initiator and the iodonium salt-type cationic photopolymerization initiator, as long as the effects of the present invention are not impaired. Examples of the other polymerization initiators include a thermal cationic polymerization initiator, a nonionic photocationic polymerization initiator, and a radical polymerization initiator.

[0157] (a) Thermal cationic polymerization initiator The thermal cationic polymerization initiator can be any existing compound that accelerates the curing reaction when the curing temperature is reached. Examples of the thermal cationic polymerization initiator include the thermal cationic polymerization initiator described in JP-A-2023-24144. Commercially available thermal cationic initiators include, for example, ADEKAOPTON CP-77 and ADEKAOPTON CP-66 (both manufactured by ADEKA Corporation); CI-2639 and CI-2624 (both manufactured by Nippon Soda Co., Ltd.); SAN-AID SI-60, SAN-AID SI-80, SAN-AID SI-B3, SAN-AID SI-B3A and SAN-AID SI-B4 (all manufactured by Sanshin Chemical Industry Co., Ltd.), CXC1612, CXC1738 and CXC1821 (all manufactured by King Industries).

[0158] In the present disclosure, from the viewpoint of improving the storage stability of the composition, The content of the thermal cationic polymerization initiator is, in 100 parts by mass of the polymerization initiator, It is preferably less than 50 parts by mass, More preferably, it is 20 parts by mass or less, It is more preferably 10 parts by mass or less, It is particularly preferable that the content is 0 part by mass, that is, that the thermal cationic polymerization initiator is not contained. The content of the thermal cationic polymerization initiator is, in 100 parts by mass of the cationic polymerization initiator, It is preferably less than 50 parts by mass, More preferably, it is 20 parts by mass or less, It is more preferably 10 parts by mass or less.

[0159] (b) Nonionic photocationic polymerization initiator Examples of the nonionic photocationic polymerization initiator include compounds described in JP-A-2022-157602. Commercially available examples of the nonionic photocationic polymerization initiator include WPAG-145, WPAG-149, WPAG-170, and WPAG-199 (all manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), D2963, F0362, M1209, and M1245 (all manufactured by Tokyo Chemical Industry Co., Ltd.), ADEKA ARCLES SP-082, ADEKA ARCLES SP-103, ADEKA ARCLES SP-601, and ADEKA ARCLES SP-606 (all manufactured by ADEKA Corporation), SIN-11 (manufactured by Sanbo Chemical Research Institute Co., Ltd.), NP-TM2, NP-SE10, and NA-CS1 (all manufactured by San-Apro Co., Ltd.).

[0160] In the present disclosure, from the viewpoint of improving the storage stability of the composition, The content of the nonionic photocationic polymerization initiator is, in 100 parts by mass of the polymerization initiator, It is preferably less than 50 parts by mass, More preferably, it is 20 parts by mass or less, It is more preferably 10 parts by mass or less, It is particularly preferable that the content is 0 part by mass, that is, that the thermal cationic polymerization initiator is not contained. The content of the nonionic photocationic polymerization initiator is, in 100 parts by mass of the cationic polymerization initiator, It is preferably less than 50 parts by mass, More preferably, it is 20 parts by mass or less, It is more preferably 10 parts by mass or less.

[0161] (c) Radical polymerization initiator The radical polymerization initiator may be a photoradical polymerization initiator or a thermal radical polymerization initiator. As the photoradical polymerization initiator or the thermal radical polymerization initiator, any known radical polymerization initiator may be used without any particular limitation, but from the viewpoint of further accelerating the polymerization reaction, it is particularly preferable to use a photoradical polymerization initiator as the radical polymerization initiator. Preferred photoradical polymerization initiators include compounds described in, for example, JP-A Nos. 2018-172495, 2018-127527, and 2017-098290, and acetophenone-based compounds are particularly preferred.

[0162] In the present disclosure, from the viewpoint of improving the cure shrinkage rate of the cured product of the composition, The content of the radical polymerization initiator is, relative to 100 parts by mass of the cationic polymerization initiator, It is preferably 300 parts by mass or less, It is more preferable that the amount is 200 parts by mass or less, It is particularly preferably 100 parts by mass or less.

[0163] (4) Polymerization initiator In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the polymerization initiator is, relative to 100 parts by mass of the curable component, It is preferably 0.1 parts by mass or more and 20 parts by mass or less, More preferably, the content is 0.5 parts by mass or more and 10 parts by mass or less, More preferably, the content is 1 part by mass or more and 10 parts by mass or less, It is particularly preferable that the amount is 2 parts by mass or more and 8 parts by mass or less. The content of the cationic polymerization initiator is, relative to 100 parts by mass of the curable component, It is preferably 0.1 parts by mass or more and 20 parts by mass or less, More preferably, the content is 0.5 parts by mass or more and 10 parts by mass or less, More preferably, the content is 1 part by mass or more and 10 parts by mass or less, It is particularly preferable that the amount is 2 parts by mass or more and 8 parts by mass or less.

[0164] In the present disclosure, from the viewpoint that the composition can easily form a cured product having excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, The content of the polymerization initiator in 100 parts by mass of the composition is It is preferably 5 parts by mass or less, More preferably, the content is 0.01 parts by mass or more and 4 parts by mass or less. More preferably, the content is 0.05 parts by mass or more and 2 parts by mass or less, It is particularly preferable that the content is 0.1 parts by mass or more and 1.5 parts by mass or less, It is particularly preferable that the amount is 0.3 parts by mass or more and 1.3 parts by mass or less. The content of the cationic polymerization initiator in 100 parts by mass of the composition is It is preferably 5 parts by mass or less, More preferably, the content is 0.01 parts by mass or more and 3 parts by mass or less, More preferably, the content is 0.05 parts by mass or more and 1.5 parts by mass or less, It is particularly preferable that the content is 0.1 parts by mass or more and 1.3 parts by mass or less, It is particularly preferable that the amount is 0.3 parts by mass or more and 1.0 parts by mass or less.

[0165] A3. Other ingredients The composition contains the curable component and the polymerization initiator, and may further contain other components as necessary. Examples of the other components include various additives such as other polymerizable compounds other than the above-mentioned curable components; sensitizers; stabilizers; inorganic compounds; coupling agents; solvents; curing accelerators; leveling agents; colorants such as pigments and dyes; antifoaming agents; thickeners; thixotropic agents; surfactants; flame retardants; plasticizers; antioxidants; polymerization inhibitors; ultraviolet absorbers; antistatic agents; flow adjusters; and adhesion promoters.

[0166] (1) Other polymerizable compounds The composition may contain other polymerizable compounds in addition to the curable components of the alicyclic epoxy compound, aromatic epoxy compound, aliphatic epoxy compound, and oxetane compound. The other polymerizable compounds are not particularly limited as long as they are components that are cured by energy ray irradiation. Examples of the other polymerizable compounds include vinyl ether compounds and acrylic compounds. The vinyl ether compound has a vinyl ether structure and can be a compound that does not have an epoxy group, an acrylic group, or an oxetanyl group. Examples of the vinyl ether compound include compounds described in JP-A-2022-42418. The acrylic compound may be a compound having an acrylic group or a methacrylic group but not having an epoxy group or an oxetanyl group. Examples of the acrylic compound include the compounds described in JP 2018-165329 A.

[0167] (2) Sensitizer The composition may contain a sensitizer to promote polymerization. The sensitizer may be any known compound without particular limitation, as long as it absorbs energy ray irradiation light and promotes decomposition of the acid generator. Two or more types of sensitizers may be used in combination. The sensitizer preferably contains at least one compound represented by the following general formula (F-1) or (F-2). This is because it has a significant effect of enhancing the sensitization performance of the composition.

[0168] [ka] (In general formulas (F-1) and (F-2), R 141 , R 142 , R 143 and R 144 each independently represents an alkyl group having 1 to 10 carbon atoms.

[0169] In the above general formulas (F-1) and (F-2), R 141 , R 142 , R 143 and R 144Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (A-1) include R 1 In the alkyl group having 1 to 20 carbon atoms, such as those represented by the formula (I), groups having a predetermined number of carbon atoms are exemplified.

[0170] In the present disclosure, from the viewpoint of improving the sensitivity of the composition, R 141 , R 142 , R 143 and R 144 teeth, It is preferably an alkyl group having 1 to 10 carbon atoms, It is more preferable that the alkyl group has 2 to 6 carbon atoms. An alkyl group having 2 to 4 carbon atoms is particularly preferred. Also, R 141 , R 142 , R 143 and R 144 may be the same group or different groups. However, in the present disclosure, R 141 and R 142 are preferably the same group, and R 143 and R 144 It is also preferable that these groups are the same, since this leads to good sensitization performance.

[0171] In the present disclosure, from the viewpoint that the composition has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and is easy to form a cured product excellent in dimensional stability and adhesive strength, it is preferable that the sensitizer contains at least one of the compounds represented by the general formulas (F-1) and (F-2), and it is more preferable that the sensitizer contains a compound represented by the general formula (F-1), and in particular, R 141 and R 142 is preferably an alkyl group having 2 to 4 carbon atoms.

[0172] The composition may use a commercially available sensitizer, such as 9,10-bis(octanoyloxy)anthracene (product name "UVS-581" manufactured by Air Water Performance Chemicals Inc.), 1,4-diethoxynaphthalene (product name "UVS-2171" manufactured by Air Water Performance Chemicals Inc.), 9,10-dibutoxyanthracene (product name "UVS-1331" manufactured by Air Water Performance Chemicals Inc.), or 9,10-diethoxyanthracene (product name "UVS-1101" manufactured by Air Water Performance Chemicals Inc.).

[0173] In the present disclosure, when the composition contains a sensitizer, the composition is able to easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from the viewpoint of: The content of the sensitizer is, relative to 100 parts by mass of the polymerization initiator, It is preferably 0.1 parts by mass or more and 15 parts by mass or less, More preferably, the content is 0.5 parts by mass or more and 10 parts by mass or less, More preferably, the content is 0.8 parts by mass or more and 8 parts by mass or less. It is particularly preferable that the amount is 1 part by mass or more and 6 parts by mass or less. The content of the sensitizer is, relative to 100 parts by mass of the cationic polymerization initiator, It is preferably 0.1 parts by mass or more and 15 parts by mass or less, More preferably, the content is 0.5 parts by mass or more and 10 parts by mass or less, More preferably, the content is 0.8 parts by mass or more and 8 parts by mass or less. It is particularly preferable that the amount is 1 part by mass or more and 6 parts by mass or less.

[0174] In the present disclosure, when the composition contains a sensitizer, the composition is able to easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from the viewpoint of: The content of the sensitizer is, relative to 100 parts by mass of the curable component, It is preferably 0.01 parts by mass or more and 10 parts by mass or less, More preferably, the content is 0.03 parts by mass or more and 5 parts by mass or less, It is particularly preferable that the amount is 0.05 part by mass or more and 1 part by mass or less.

[0175] (4) Inorganic compounds In the present disclosure, inorganic compounds may be included as needed. Examples of the inorganic compounds include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt-based compounds, manganese-based compounds, glass powder, mica, talc, kaolin, ferrocyanides, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, and copper. Among these, titanium oxide and silica are preferably used, and hydrophobic silica and silica filler are more preferably used, from the viewpoint that the composition can easily form a cured product having excellent dimensional stability.

[0176] In the present disclosure, when the composition contains the inorganic compound, the composition is able to easily form a cured product that has excellent deep curing properties, a small cure shrinkage rate, and an excellent balance between a high glass transition point, dimensional stability, and adhesive strength, and from this viewpoint, The content of the inorganic compound is, relative to 100 parts by mass of the curable component, It is preferably 50 parts by mass or more and 1,000 parts by mass or less, More preferably, the content is 100 parts by mass or more and 800 parts by mass or less, More preferably, the content is 200 parts by mass or more and 700 parts by mass or less, It is particularly preferable that the content is 300 parts by mass or more and 650 parts by mass or less.

[0177] When the composition contains the inorganic compound, the composition is excellent in deep curing properties, has a small cure shrinkage rate, and is easily able to form a cured product having a high glass transition point, dimensional stability, and adhesive strength, and from the viewpoint of: The content of the inorganic compound in 100 parts by mass of the composition is It is preferably 1 part by mass or more and 95 parts by mass or less, More preferably, the content is 5 parts by mass or more and 90 parts by mass or less, More preferably, the content is 10 parts by mass or more and 85 parts by mass or less, It is particularly preferable that the amount is 30 parts by mass or more and 80 parts by mass or less.

[0178] (5) Coupling agent The composition may contain a coupling agent to improve adhesion to the substrate, such as the compounds described in Japanese Patent No. 7043142. Commercially available coupling agents include, for example, 1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-573, KBM-575, KBM-6123, and KBE Examples of the coupling agent include KBM-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007, KBM-04, KBE-04, KBM-13, KBE-13, KBE-22, KBE-103, HMDS-3, KBM-3063, KBM-3103C, KPN-3504, KF-99, KBM-6803, KBM-4803, KBM-1083, and KBM-5803 (all manufactured by Shin-Etsu Silicones). The coupling agent is preferably a silane coupling agent, and more preferably a compound having an epoxy group.

[0179] When the composition contains the coupling agent, the composition is easily able to form a cured product that has excellent deep curing properties, a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength, and from the viewpoint of: The content of the coupling agent in 100 parts by mass of the composition is It is preferably 0.05 parts by mass or more and 20 parts by mass or less, More preferably, the amount is 0.1 parts by mass or more and 10 parts by mass or less, It is particularly preferable that the content be 0.3 parts by mass or more and 3 parts by mass or less.

[0180] A4.Blending method The method for producing the composition may be any method capable of forming a composition containing the desired amounts of each of the components, and may include a method using a known mixing means. For example, the composition may be produced by mixing the components using a mixer such as a homodisper, a homomixer, a universal mixer, a planetary mixer, a kneader, or a three-roll mill.

[0181] A5.Application The use of the composition is not particularly limited, and it can be used in various applications in which conventional epoxy resin compositions are used. In particular, it is suitable for various applications such as automobile interiors, electronic and electrical equipment, building panels, furniture and woodworking, bookbinding, and textile processing. Since the composition has excellent deep curing properties and can form a cured product with excellent adhesive strength, it can be particularly suitable for use in adhesive applications such as adhesives for optical materials and adhesives for peripheral parts of optical materials.

[0182] Examples of the optical material include photographic lenses for cameras (such as in-vehicle cameras, digital cameras, PC cameras, mobile phone cameras, and surveillance cameras), eyeglass lenses, filters, diffraction gratings, prisms, light beam focusing lenses, light diffusing lenses, cover glass for display devices, photosensors, photoswitches, LEDs, light-emitting elements, optical waveguides, light splitters, adhesives for optical fibers, substrates for display devices, substrates for color filters, substrates for touch panels, display protective films, display backlights, light guide plates, light-shielding filters, and anti-reflection films. The composition can be particularly suitably used for camera lenses.

[0183] Other uses of the above compositions include, for example, optical filters including light-shielding filters; paints; coating agents; lining agents; printing plates; insulating varnishes; insulating sheets; laminates; printed wiring boards; sealants for semiconductor devices, LED packages, liquid crystal injection ports, organic electroluminescence (EL), optical elements, electrical insulation, electronic components, separation membranes, etc.; molding materials; putties, glass fiber impregnating agents; fillers; passivation films for semiconductors, solar cells, etc.; interlayer insulating films; protective films; color filters for color televisions, PC monitors, personal digital assistants, and CCD image sensors; electrode materials for plasma display panels; printing inks; dental compositions; resins for stereolithography; both liquid and dry films; micromechanical parts; glass fiber cable coating materials; and holographic recording materials.

[0184] When the composition is used as an adhesive, the substrate to be adhered to the composition is not particularly limited, but examples thereof include metal materials, polymeric materials, wood materials, paper materials, and inorganic materials. Examples of the metal material include iron, copper, aluminum, titanium, tinplate, stainless steel, mild steel, plated steel, painted steel sheet, and galvanized steel sheet. Examples of the polymeric material include cellulose esters such as diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, acetylpropionyl cellulose, and nitrocellulose; polyamide (nylon); polyurethane; epoxy resin; polycarbonate; polyesters such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4'-dicarboxylate, and polybutylene terephthalate; and polystyrene. styrene-based resins such as ABS resin; olefin-based resins such as polyethylene, polypropylene, and polymethylpentene; vinyl-based resins such as polyvinyl acetate, polyvinyl chloride, and polyvinyl fluoride; acrylic resins such as polymethyl methacrylate and polyacrylate; polycarbonate; engineering plastics such as amorphous polyarylate, polysulfone, polyethersulfone, polyphenylene sulfide, polyetheretherketone, polyimide, polyetherimide, and fluororesin; and cyclic polymers such as norbornene resin and cycloolefin polymer (COP). Examples of the wood material include wood, plywood, particle board, and MDF. Examples of the paper material include plain paper, reinforced paper, resin-impregnated paper, and cardboard. Examples of the inorganic material include gypsum board and calcium silicate board. In the present disclosure, the substrate is preferably a metal material or a polymer material, more preferably a metal material or an engineering plastic, and particularly preferably a metal material, because this provides good adhesion to the composition.

[0185] B. Cured product Next, the cured product will be described. The cured product is a cured product of the above-mentioned composition.

[0186] Since the above-mentioned cured product uses the above-mentioned composition, it is possible to form a cured product that has excellent deep curing properties, a small shrinkage rate after curing, a high glass transition point, and excellent dimensional stability and adhesiveness. The composition of the cured product can be the same as that described in the section "A. Composition" above, and therefore a description thereof will be omitted here. The uses of the cured product may be the same as those described in the section "A. Composition" above.

[0187] The method for producing the cured product may be any method that can cure the composition. The method for producing the cured product may be the method described below in "C. Method for producing a cured product."

[0188] C. Manufacturing method of cured product Next, a method for producing the cured product will be described. The method for producing the cured product is characterized by having a curing step of curing the curable component in the composition.

[0189] According to the present invention, since the above-mentioned composition is used, it is possible to easily obtain a cured product that has a small cure shrinkage rate, a high glass transition point, and excellent dimensional stability and adhesive strength.

[0190] C1.Curing process This step is a step of curing the composition. In this step, any method can be used as long as it can polymerize one or more of the curable components in the composition, and examples include a method in which a coating film of the composition is irradiated with light (energy rays) to polymerize it.

[0191] Examples of light sources for the light energy rays include high-energy rays such as electromagnetic wave energy having a wavelength of 2,000 angstroms or more and 7,000 angstroms or less, electron beams, X-rays, and radioactive rays, which are obtained from ultra-high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light-emitting diodes, and CRT light sources. The light source used in this step is preferably an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a light-emitting diode, or the like, which emits light with a wavelength of 300 to 450 nm, since this makes it easier to control the curing reaction of the composition.

[0192] The irradiation dose of the energy ray is not particularly limited and can be determined appropriately depending on the composition of the composition. From the viewpoint of preventing deterioration of the composition, the irradiation dose is set to 100 mJ / cm at 365 nm. 2 More than 2,000mJ / cm 2 It is preferable that:

[0193] In this step, the curing method may be any method that includes a method of irradiating the coating film with active energy rays, and may also be a method of heating the coating film.

[0194] Examples of methods for heating the coating include methods using a hot plate such as a hot plate, an atmospheric oven, an inert gas oven, a vacuum oven, and a hot air circulation oven. When the coating film is heated, the heating temperature is not particularly limited, but from the viewpoint of easily controlling the curing reaction of the composition, it is preferably 70°C or higher and 200°C or lower, and particularly preferably 90°C or higher and 150°C or lower. The time for heating the coating film is not particularly limited, but from the viewpoint of improving productivity, it is preferably from 10 seconds to 3 hours, more preferably from 20 seconds to 2 hours and 30 minutes, and even more preferably from 30 seconds to 2 hours.

[0195] C2. Other processes The above manufacturing method may include other steps as necessary. Examples of other steps include a coating step of coating the composition onto a substrate prior to the above-mentioned "C1. curing step." In the coating step, the composition can be applied to the substrate by any known method, such as using a spin coater, roll coater, bar coater, die coater, curtain coater, various printing methods, and dipping.

[0196] The substrate can be appropriately selected depending on the application of the cured product, and is not particularly limited, and any commonly used substrate can be used. The substrate can be the same as that described in the section "A6. Composition" above. The cured product of the present invention may be formed on the above-mentioned substrate and then peeled off from the substrate for use, or may be transferred from the substrate to another substrate for use.

[0197] D. Other The present invention includes the following embodiments [1] to [6]. [1] a curable component; a sulfonium salt-type cationic photopolymerization initiator; an iodonium salt-type photocationic polymerization initiator, The composition, wherein the curable component comprises an alicyclic epoxy compound, at least one selected from an aromatic epoxy compound and an aliphatic epoxy compound, and an oxetane compound. [2] The composition according to [1], wherein the sulfonium salt-type photocationic polymerization initiator and the iodonium salt-type photocationic initiator have an anion containing a boron atom. [3] The content of the sulfonium salt-type photocationic polymerization initiator is 0.05 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the curable component, The content of the iodonium salt-type photocationic polymerization initiator is The composition according to [1] or [2], wherein the amount is 0.05 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the curable component. [4] The composition according to any one of [1] to [3], further comprising a sensitizer. [5] A cured product of the composition according to any one of [1] to [4]. [6] A method for producing a cured product, comprising a step of curing the composition according to any one of [1] to [4].

[0198] The present invention is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and that provides similar effects is included within the technical scope of the present invention. [Example]

[0199] [Examples 1 to 27, Comparative Examples 1 and 2] Compositions were obtained by mixing the components according to the formulations in Tables 1 to 4 below. The following materials were used for each component. The blend amounts in the table represent parts by mass of each component.

[0200] Component (A): Alicyclic epoxy compound A1: Epocalic (registered trademark) THI-DE (product of ENEOS Corporation, compound represented by general formula (A-1))

[0201] [ka]

[0202] A2: DCA (manufactured by ADEKA Corporation, compound represented by general formula (A-5))

[0203] [ka]

[0204] A3: Celloxide 2021P (a product manufactured by Daicel Chemical Industries, Ltd., a compound represented by general formula (A-5))

[0205] [ka]

[0206] Component (B): Aromatic epoxy compound B1: Bisphenol A diglycidyl ether (aromatic bifunctional epoxy compound, compound represented by general formula (B-1))

[0207] [ka]

[0208] B2: TECHMORE VG3101L (manufactured by Air Water Inc., aromatic polyfunctional epoxy compound, compound represented by general formula (B-5))

[0209] [ka] (a mixture of 90 wt% EP1 and 10 wt% EP2)

[0210] B3: jER1001 (bisphenol A type epoxy resin, aromatic bifunctional epoxy compound, compound represented by general formula (B-1), manufactured by Mitsubishi Chemical Corporation) Component (C): Aliphatic epoxy compound C1: EHPE-3150 (a product of Daicel Corporation, an aliphatic epoxy compound, an aliphatic ring-containing epoxy compound, a compound represented by general formula (C-2))

[0211] [ka] (Epoxy equivalent: 170-190)

[0212] Component (D): Oxetane compound D1: ETERNACOLL OXBP (manufactured by UBE Corporation, aromatic oxetane compound, compound represented by general formula (D-1))

[0213] [ka] (The main component is a compound with n1=1)

[0214] D2: Aron Oxetane OXT-121 (a product of Toagosei Co., Ltd., an aromatic oxetane compound, a compound represented by general formula (D-1))

[0215] [ka]

[0216] D3: Aron Oxetane OXT-191 (a product of Toagosei Co., Ltd., an aliphatic oxetane compound, a compound represented by general formula (D-2))

[0217] [ka] (n2 represents an integer of 1 to 4.)

[0218] D4: Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd., an aliphatic oxetane compound, a compound represented by general formula (D-2))

[0219] [ka]

[0220] Component (E): Polymerization initiator E1: TR-PAG-20108 (Dongguan product, sulfonium salt type photocationic polymerization initiator, anion is (C6F5)4B - ) E2: TR-PAG-30408 ​​(Dongguan product, iodonium salt type photocationic polymerization initiator, anion is (C6F5)4B - ) E3: San-Aid SI-B3 (manufactured by Sanshin Chemical Industry Co., Ltd.), a thermal cationic polymerization initiator, with an anion of (C6F5)4B - ) E4: Ominirad184 (product of IGM Resins BV, photoradical polymerization initiator, acetophenone-based compound) E5: Ominirad2959 (product of IGM Resins BV, photoradical polymerization initiator, acetophenone-based compound)

[0221] (F) Other ingredients F1: Anthracure UVS-2171 (product of Air Water Performance Chemicals, sensitizer) F2: San-Aid SI-S (product of Sanshin Chemical Industry Co., Ltd., stabilizer) F3: KBM-403 (product of Shin-Etsu Chemical Co., Ltd., coupling agent) F4: KBM-4803 (product of Shin-Etsu Chemical Co., Ltd., coupling agent) F5: FBE25K-SED (product of Admatechs Co., Ltd., inorganic compound, silica filler) F6: 200SE-E1 (product of Admatechs Co., Ltd., inorganic compound, silica filler) F7: VP NKC-130 (Nippon Aerosil Co., Ltd. product, inorganic compound, hydrophobic silica)

[0222] <Evaluation> The resulting compositions were evaluated for cure shrinkage (%), Tg of the cured product, coefficient of linear expansion, deep curability, and adhesive strength according to the following procedures. The results are shown in Tables 1 to 4.

[0223] (1) Curing shrinkage rate (%) Each composition was applied to a glass substrate and illuminated with an LED light source (1,000 mW / cm ) with a wavelength of 365 nm. 2 ) at 2,000mJ / cm 2After exposure, the coating was heat-cured at 120°C for 1 hour to obtain a cured product. The cured product was peeled off from the glass substrate to obtain a measurement sample (film thickness 1 mm x width 5 mm). The density of each of the obtained sample and the sample before curing was measured using a gas pycnometer (JIS Z8837). The cure shrinkage (%) was calculated from the rate of change in density before and after curing and evaluated according to the following criteria. The results are shown in Tables 1 to 4. A cured product with a low cure shrinkage rate has excellent dimensional stability and can be suitably used, for example, as an adhesive requiring high positional accuracy.

[0224] (Evaluation method) ++: Curing shrinkage is less than 2%. +: Curing shrinkage is 2% or more and less than 3%. -: Curing shrinkage rate is 3% or more.

[0225] (2) Cured product Tg (℃) Each composition was applied to a glass substrate and illuminated with an LED light source (1,000 mW / cm ) with a wavelength of 365 nm. 2 ) at 2,000mJ / cm 2 After exposure, the coating was heated and cured at 120°C for 1 hour to obtain a cured product, which was then peeled off from the glass substrate to obtain a measurement sample (film thickness 1 mm x width 0.6 mm). The glass transition temperature (Tg) of the obtained measurement sample was measured using a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science Corp., and evaluated according to the following criteria. The results are shown in Tables 1 to 4 below. A cured product with a high Tg (°C) has excellent heat resistance and durability against temperature changes.

[0226] (Evaluation method) ++: Glass transition point is over 120°C. +: Glass transition point is over 100°C and below 120°C. -: Glass transition point is below 100°C.

[0227] (3) Linear expansion coefficient (10 -6 / ℃) Each composition was applied to a glass substrate and illuminated with an LED light source (1,000 mW / cm ) with a wavelength of 365 nm. 2 ) at 2,000mJ / cm 2 After exposure, the coating was heated and cured at 120°C for 1 hour to obtain a cured product, which was then peeled off from the glass substrate to obtain a measurement sample (film thickness 1 mm x width 3 mm). The obtained measurement sample was measured for linear expansion coefficient (10 -6 / °C) was measured and evaluated according to the following criteria. The results are shown in Tables 1 to 4 below. Note that a cured product with a low coefficient of linear expansion has excellent dimensional stability and can be suitably used, for example, as an adhesive with high positional accuracy.

[0228] (Measurement conditions) Measurement temperature: -20℃~250℃ Heating rate: 5℃ / min

[0229] (Evaluation method) ++:35ppm or less. +: More than 35ppm and less than 50ppm. -:Over 50ppm.

[0230] (4) Deep hardening (mm) Each composition was filled into a tube with a pore diameter of 3 mm, and an LED light source with a wavelength of 365 nm (1,000 mW / cm ) was applied from one end of the tube. 2 ), 2,000mJ / cm 2 The resulting cured product was taken out of the tube, and the distance from the exposed surface to the tip of the cured product was measured and evaluated according to the following criteria. The results are shown in Tables 1 to 4 below. A composition with high deep curability has excellent curability.

[0231] (Evaluation method) ++: 1.0mm or more. +: 0.5mm or more but less than 1.0mm. -:Less than 0.5mm.

[0232] (5) Adhesion strength (adhesion to metal materials) On aluminum as a metal material, the coating amount is 10 mm 3 Each composition was applied so that the thickness was 100 μm, and then the composition was exposed to a 365 nm wavelength LED light source (1,000 mW / cm 2 ) at 2,000mJ / cm 2 After exposure, the film was heat-cured at 120°C for 1 hour to obtain a test piece. The adhesive strength (MPa) was then measured using a Nordson DAGE 4000Plus and evaluated according to the following criteria. The results are shown in Tables 1 to 4 below.

[0233] (Evaluation method) ++: 5MPa or more. +: 3MPa or more but less than 5MPa. -:Less than 3MPa.

[0234] (6) Adhesion strength (adhesion strength to polymer materials) The coating amount is 10 mm on PPS (polyphenylene sulfide resin) as a polymer material. 3 Each composition was applied so that the thickness was 100 μm, and then the composition was exposed to a 365 nm wavelength LED light source (1,000 mW / cm 2 ) at 2,000mJ / cm 2 After exposure, the coating was heat-cured at 120°C for 1 hour to obtain a test piece. The adhesive strength (MPa) was then measured using a Nordson DAGE 4000Plus and evaluated according to the following criteria. The results are shown in Tables 1 to 4 below.

[0235] (Evaluation method) ++: 5MPa or more. +: 3MPa or more but less than 5MPa. -:Less than 3MPa.

[0236] (7) Storage stability Each composition was placed in a transparent sample bottle and stored at room temperature for 5 days, and the viscosity of each composition was measured before and after storage and evaluated according to the following criteria. The results are shown in Tables 1 to 4.

[0237] (Evaluation method) +: The increase in viscosity before and after storage is within 10%. -: The increase in viscosity before and after storage is more than 10%.

[0238] [Table 1]

[0239] [Table 2]

[0240] [Table 3]

[0241] [Table 4]

[0242] From the results in Tables 1 to 4, it was confirmed that the compositions of the examples were capable of forming cured products with excellent deep curing properties, small cure shrinkage, high glass transition points, and excellent dimensional stability and adhesive strength.

Claims

1. A curable component; a sulfonium salt-type cationic photopolymerization initiator; an iodonium salt-type photocationic polymerization initiator, The composition, wherein the curable component comprises an alicyclic epoxy compound, at least one selected from an aromatic epoxy compound and an aliphatic epoxy compound, and an oxetane compound.

2. The composition according to claim 1 , wherein the sulfonium salt-type cationic photopolymerization initiator and the iodonium salt-type cationic photopolymerization initiator each have an anion containing a boron atom.

3. The content of the sulfonium salt type photocationic polymerization initiator is 0.05 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the curable component, The content of the iodonium salt-type photocationic polymerization initiator is 0.05 parts by mass or more and 20 parts by mass or less relative to 100 parts by mass of the curable component; The composition of claim 1.

4. The composition of claim 1 further comprising a sensitizer.

5. A cured product of the composition according to any one of claims 1 to 4.

6. A method for producing a cured product, comprising the step of curing the composition according to any one of claims 1 to 4.

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