Composition and cured product

Abstract

To provide a composition having excellent heat resistance property of a cured product and curable property of a composition.SOLUTION: A composition contains the following component (A), component (B) and component (C). Component (A): alicyclic epoxy compound, component (B): trifunctional or more oxetane compound, and component (C): bifunctional oxetane compound and / or monofunctional oxetane compound. It is preferable that the alicyclic epoxy compound includes at least one kind selected from a compound having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure, and a compound having a structure in which two cycloalkene oxide structures are linked by a linking group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a composition and its cured product. [Background technology]

[0002] Epoxy resins possess excellent thermal, mechanical, and electrical properties, and their application is progressing in various fields such as electrical and electronic equipment materials, mechanical materials, civil engineering and construction materials, and everyday goods. However, as the use of epoxy resins in advanced technology fields is being considered, such as high-performance composite materials with carbon fibers used as structural materials for aircraft, and electronic materials such as printed circuit boards and IC encapsulants, there is a demand for higher-performance resins, and various improvements are being attempted. The performance characteristics that are being sought include improvements in curability and heat resistance. Such performance improvements are difficult to achieve through improvements to epoxy resins alone, and numerous attempts have been made to improve them by combining epoxy resins with other resins.

[0003] For example, Patent Document 1 proposes a curable composition containing a glycidyl compound of a polyhydric alcohol glycidyl or polyhydric alcohol alkylene oxide adduct, an oxetane compound, a specific radical polymerizable component, and a specific radical polymerization initiator. Patent Document 2 proposes a curable composition containing a polyhydric alcohol glycidylate, an alicyclic epoxy compound, a cationic polymerization initiator, a radical polymerizable component having an epoxy group, a radical polymerization initiator, and a specific polymer. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-26774 [Patent Document 2] Japanese Patent Publication No. 2017-179161 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, even with the curable compositions proposed in Patent Documents 1 and 2, the heat resistance and curability of the cured product were not always satisfactory. Therefore, a composition with excellent heat resistance and curability of the cured product is desired.

[0006] This invention has been made in view of the above circumstances, and aims to provide a composition that exhibits excellent heat resistance of the cured product and curability of the composition. [Means for solving the problem]

[0007] The inventors of the present invention diligently studied to solve the above problems and found that the above problems can be resolved by a composition having a specific composition, thus completing the present invention.

[0008] In other words, the present invention provides a composition containing the following components (A), (B), and (C). (A) Components: Alicyclic epoxy compound and (B) Component: Trifunctional or greater oxetane compound, (C) Component: Difunctional oxetane compound and / or monofunctional oxetane compound

[0009] According to the present invention, it is possible to form a cured product with excellent heat resistance and to provide a composition with excellent curability.

[0010] In the present invention, it is preferable that component (A) contains at least one compound represented by the following general formulas (A-1), (A-2), (A-3), (A-4), and (A-5). The above composition can form a cured product with even better heat resistance, and therefore exhibits excellent curability.

[0011] [ka]

[0012] In formula (A-1), R 40 , 36 , 37 , 38 , 39 , 35 , 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 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0013]

Chemical formula

[0014] In formula (A-2), R 11 , R 12 , R 13 , R 14 , R[[ID=(42]] 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 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms.

[0015] <0(000391>

Chemical formula

[0016] In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0017] [ka]

[0018] In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0019] [ka]

[0020] In 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 , R84 , R 85 , R 86 , R 87 and R 88 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Z represents a single bond, an alkylene group with 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group consisting of multiple such bonds.

[0021] In the present invention, it is preferable that component (B) is a compound represented by the following general formula (B1). The above composition can form a cured product with even better heat resistance, and therefore exhibits excellent curability.

[0022] [ka]

[0023] In formula (B1), X represents an oxetanyl group represented by the following general formula (X), n1 represents a number between 1 and 10 (inclusive).

[0024] [ka]

[0025] In equation (X), * represents the bond position between X and an adjacent oxygen atom. L 1 This represents an alkylene group having 1 to 10 carbon atoms, and some of the methylene groups of the alkylene group may be substituted with oxygen atoms. R B1 This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have further substituents.

[0026] In the present invention, it is preferable that the content of component (A) is 0.5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of solid content of the composition. This is because by keeping the content within the above numerical range, the composition can form a cured product with excellent heat resistance and thus excellent curability.

[0027] In the present invention, it is preferable that the content of component (B) is 10 parts by mass or more and 75 parts by mass or less per 100 parts by mass of solid content of the composition. By setting the content within the above numerical range, the composition can form a cured product with excellent heat resistance and thus excellent curability.

[0028] In the present invention, it is preferable that the content of component (C) is 1 part by mass or more and 60 parts by mass or less per 100 parts by mass of solid content of the composition. By keeping the numerical range as described above, the composition can form a cured product with excellent heat resistance and thus excellent curability.

[0029] In the present invention, it is preferable to further include a polymerization initiator as component (D), because it can accelerate the curing reaction of the above composition.

[0030] The present invention provides a cured product of the above-described composition. [Effects of the Invention]

[0031] According to the present invention, it is possible to form a cured product with excellent heat resistance and to provide a composition with excellent curability. [Modes for carrying out the invention]

[0032] This invention relates to a composition and its cured product. The compositions and cured products of the present invention will be described in detail below.

[0033] In this specification, the number of carbon atoms in a group refers to the number of carbon atoms in the group after substitution, if a hydrogen atom in the group is substituted by a substituent. For example, if a hydrogen atom in an alkyl group having 1 to 20 carbon atoms is substituted, the number of carbon atoms, from 1 to 20, refers to the number of carbon atoms after the hydrogen atom substitution, and not to the number of carbon atoms before the hydrogen atom substitution. Furthermore, in this specification, the specification for the number of carbon atoms in a group in which a methylene group has a predetermined number of carbon atoms is replaced by a divalent group refers to the number of carbon atoms in the group after substitution.

[0034] In this specification, "solids content of the composition" refers to the total content of all components in the composition excluding the solvent.

[0035] A. Composition First, the composition of the present invention will be described. The composition of the present invention comprises the following components (A), (B), and (C). (A) Component: Alicyclic epoxy compound (B) Component: Trifunctional or higher oxetane compound (C) Component: Difunctional oxetane compound and / or monofunctional oxetane compound

[0036] The following describes each component that constitutes the composition of the present invention.

[0037] A1. Alicyclic epoxy compounds The composition of the present invention contains an alicyclic epoxy compound as component (A). The above component (A) is a compound having at least one alicyclic epoxy group in its molecule, i.e., a compound having a cycloalkene oxide structure, and may have multiple alicyclic epoxy groups in one molecule, or may have epoxy groups other than alicyclic epoxy groups. Furthermore, the above component (A) may be used in combination of two or more alicyclic epoxy compounds. The above-mentioned cycloalkene oxide structure refers to a structure in which an aliphatic ring and an epoxy ring share a portion of the ring structure, such as a cyclohexene oxide structure or a cyclopentene oxide structure, obtained by epoxidizing a cyclohexene ring-containing compound or a cyclopentene ring-containing compound with an oxidizing agent. In the present invention, compounds having an aromatic ring are also included in component (A) above, as long as they have an alicyclic epoxy group.

[0038] Examples of compounds among the above-mentioned component (A) that have one of the above-mentioned cycloalkene oxide structures include 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, dicyclopentadiene diepoxide, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, and 1,2-epoxy-2-epoxyethylcyclohexane.

[0039] Furthermore, compounds having two cycloalkene oxide structures include compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure, and compounds having a structure in which two cycloalkene oxide structures are linked by a linking group. Specific examples of compounds having a structure in which two cycloalkene oxide structures are condensed directly or via a cycloalkane structure include compounds represented by the following general formulas (A-1) to (A-4), and a specific example of a compound having a structure in which two cycloalkene oxide structures are linked by a linking group is the compound represented by the following formula (A-5).

[0040] [ka]

[0041] In formula (A-1), R 1 , R 2 , R 3 , R 4 , R5 , R 6 , R 7 , R 8 , R 9 and R 10 each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0042]

Chemical formula

[0043] In 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 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0044]

Chemical formula

[0045] In 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 , R46 , R 47 and R 48 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0046] [ka]

[0047] In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0048] [ka]

[0049] In 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 88Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Z represents a single bond, an alkylene group with 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group consisting of multiple such bonds.

[0050] The above-mentioned "groups formed by the linkage of multiple such groups" can refer to groups selected from alkylene groups, carbonyl groups, ether bonds, ester bonds, carbonate groups, and amide groups, in which groups other than alkylene groups are linked together so as not to be adjacent to each other. Furthermore, two or more groups of the same type may be combined, such as ester bond-alkylene group-ester bond-alkylene group.

[0051] In the above formula (A-1), R 1 ~R 10 , R in the above formula (A-2) 11 ~R 28 , R in the above formula (A-3) 31 ~R 48 , R in the above formula (A-4) 51 ~R 68 and R in formula (A-5) above 71 ~R 88 Examples of halogen atoms represented by this formula include fluorine, chlorine, bromine, and iodine atoms.

[0052] In the above formula (A-1), R 1 ~R 10 , R in the above formula (A-2) 11 ~R 28 , R in the above formula (A-3) 31 ~R 48 , R in the above formula (A-4) 51 ~R 68 and R in formula (A-5) above 71 ~R 88Examples of alkyl groups with 1 to 20 carbon atoms represented by include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tert-heptyl group, octyl group, isooctyl group. Examples include tyl group, tert-octyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, 4-ethyloctyl group, 1,3,5,7-tetramethyloctyl group, tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-eicosyl group, etc.

[0053] In the above formula (A-1), R 1 ~R 10 , R in the above formula (A-2) 11 ~R 28 , R in the above formula (A-3) 31 ~R 48 , R in the above formula (A-4) 51 ~R 68 and R in formula (A-5) above 71 ~R 88The alkoxy groups represented by , which have 1 to 20 carbon atoms, include methoxy, ethoxy, propoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy, 2-ethylhexyloxy, tert-octyloxy, nonyloxy, isononyloxy, and decibels. Examples include ruoxy group, isodecyloxy group, n-undecyloxy group, 1-methyldecyloxy group, n-dodecyloxy group, 4-ethyloctyloxy group, 1,3,5,7-tetramethyloctyloxy group, n-tridecyloxy group, 1-hexylheptyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, and n-eicosyloxy group.

[0054] The alkylene group represented by Z in formula (A-5) above, having 1 to 4 carbon atoms, is a group obtained by removing one hydrogen atom from an alkyl group having 1 to 4 carbon atoms, and the alkyl group is R in formula (1-1) above. 1 ~R 10 Among the alkyl groups listed as represented by , groups having a predetermined number of carbon atoms are included. Specifically, examples include the methylene group, methylmethine group, isopropylidene group, dimethylmethine group, ethylene group, trimethylene group, tetramethylene group, etc. Some or all of the hydrogen atoms of the above alkylene group may be substituted with fluorine atoms.

[0055] If Z is a group formed by linking multiple groups selected from alkylene groups, carbonyl groups, ether bonds, ester bonds, carbonate groups, and amide groups, each having 1 to 4 carbon atoms, the total number of carbon atoms in Z can be between 2 and 20. A single bond is a direct bond between carbon atoms linked by Z. An example of a compound in which two cycloalkene oxide rings are bonded by such a single bond is the compound represented by the following formula (A-6).

[0056] [ka]

[0057] Examples of methods for producing the compounds represented by the above formulas (A-1) to (A-5) include the method described in Japanese Patent Publication No. 2019-189844. Examples of commercially available compounds represented by the above formula (A-1) include THI-DE (manufactured by ENEOS Corporation). Examples of commercially available compounds represented by the above formula (A-2) include DE-102 (manufactured by ENEOS Corporation). Examples of commercially available compounds represented by the above formula (A-3) include DE-103 (manufactured by ENEOS Corporation). Examples of commercially available compounds represented by the above formula (A-5) include Celoxide 2021P and Celoxide (registered trademark) 8000 (manufactured by Daicel Corporation).

[0058] In the present invention, it is preferable that component (A) has two or more cycloalkene oxide structures, and more preferably two. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0059] The number of epoxy groups in component (A) above is preferably 2 or more and 5 or less, more preferably 2 or more and 3 or less, and particularly preferably 2. The above composition can form a cured product with excellent heat resistance and exhibits excellent curability. The number of epoxy groups in component (A) above includes the number of epoxy groups other than those in the cycloalkene oxide structure.

[0060] In the present invention, it is preferable that component (A) contains a compound having a structure in which two cycloalkene oxide structures are directly condensed, or a compound having a structure in which two cycloalkene oxide structures are linked by a linking group. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0061] In the present invention, it is preferable that the alicyclic epoxy compound contains at least one compound selected from the compounds represented by formulas (A-1), (A-2), (A-3), (A-4), and (A-5), and more preferably at least one compound selected from the compounds represented by formulas (A-1), (A-2), and (A-5), and particularly preferably at least one compound represented by formulas (A-1) and (A-5). This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0062] In the above formula (A-1), R 1 ~R 10 , R in the above formula (A-2) 11 ~R 28 , R in the above formula (A-3) 31 ~R 48 , R in the above formula (A-4) 51 ~R 68 and R in formula (A-5) above 71 ~R 88 Each of these is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and particularly preferably a hydrogen atom. The above composition can form a cured product with excellent heat resistance and has excellent curability.

[0063] In the above formula (A-5), Z is preferably a single bond, an alkylene group having 1 to 4 carbon atoms, an ester bond, or a group formed by linking an alkylene group having 1 to 4 carbon atoms with an ester bond. In particular, it is preferably a single bond or a group formed by linking an alkylene group having 1 to 4 carbon atoms with an ester bond. Especially, it is preferably a single bond or a group formed by linking an alkylene group having 1 to 2 carbon atoms with an ester bond. In particular, it is especially preferably a group formed by linking an alkylene group having 1 to 2 carbon atoms with an ester bond. The above composition can form a cured product with excellent heat resistance and exhibits excellent curability.

[0064] The molecular weight of the compound as component (A) above is preferably 100 to 400, more preferably 120 to 300, and especially preferably 150 to 255. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0065] The epoxy equivalent of the compound as component (A) above is preferably 50 g / eq. to 200 g / eq., more preferably 60 g / eq. to 150 g / eq., and particularly preferably 70 g / eq. to 130 g / eq. This is because, being within the above numerical range, the above composition can form a cured product with excellent heat resistance and thus excellent curability.

[0066] The content of component (A) above is preferably 0.5 parts by mass or more and 80 parts by mass or less in 100 parts by mass of the total of components (A), (B), and (C), more preferably 1 part by mass or more and 70 parts by mass or less, particularly preferably 3 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and even more preferably 8 parts by mass or more and 35 parts by mass or less. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0067] The content of component (A) above is preferably 0.5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of solid content of the above composition, more preferably 1 part by mass or more and 70 parts by mass or less, particularly preferably 3 parts by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, and even more preferably 8 parts by mass or more and 30 parts by mass or less. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0068] A2. Oxetane compounds with three or more functions The composition of the present invention contains a trifunctional or more oxetane compound as component (B). The above-mentioned trifunctional or more oxetane compounds refer to compounds that have three or more oxetanyl groups as functional groups in their molecule. The above trifunctional or more oxetane compounds may have functional groups other than the oxetanyl group. Examples of functional groups other than the oxetanyl group include reactive functional groups such as cationic polymerizable groups and radical polymerizable groups other than the oxetanyl group, and non-reactive functional groups such as alkyl groups. However, component (B) does not include those corresponding to component (A) above.

[0069] Aside from the oxetanyl group mentioned above, there are no restrictions on cationic polymerizable groups as long as they can be polymerized by a cation. Examples include epoxy groups other than alicyclic epoxy groups, glycidyl groups, vinyl ether groups, and the like.

[0070] The above-mentioned radical polymerizable groups are not limited as long as they can be polymerized by radicals, and examples include ethylenically unsaturated bonding groups such as acryloyl groups, methacryloyl groups, and vinyl groups.

[0071] In the present invention, the number of oxetanyl groups in the compound of component (B) is preferably 30 or less, more preferably 25 or less, particularly preferably 16 or less, and most preferably 13 or less. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0072] Specific examples of component (B) above include, for example, compounds obtained by oxetaneting resins having three or more hydroxyl groups, such as novolac resins, poly(p-hydroxystyrene), calixarenes, calixresorcinarenes, or silsesquioxane; unsaturated monomers having an oxetanyl group (for example, resins containing an oxetanyl group-containing (meth)acrylate as a constituent unit); and compounds having a siloxane structure (Si-O), such as tri[(oxetan-3-yl)methyl]methoxysilane, tri[(oxetan-3-yl)methyl]ethoxysilane, and tri[(oxetan-3-yl)methyl]acetoxysilane.

[0073] Examples of commercially available products of component (B) above include Aronoxetane OXT-191 and OX-SQ (both manufactured by Toagosei Co., Ltd.).

[0074] In the present invention, component (B) is preferably a compound having a siloxane structure (Si-O), and more preferably a compound represented by the following general formula (B1). This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0075] [ka]

[0076] In formula (B1), X represents an oxetanyl group represented by the following general formula (X), n1 represents a number between 1 and 10 (inclusive).

[0077] [ka]

[0078] In equation (X), * represents the bond position between X and an adjacent oxygen atom. L 1This represents an alkylene group having 1 to 10 carbon atoms, and some of the methylene groups of the alkylene group may be substituted with oxygen atoms. R B1 This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have further substituents.

[0079] In the above general formula (X), L 1 As an alkylene group having 1 to 10 carbon atoms represented by R in the section "A1. Alicyclic epoxy compounds" 1 Examples include groups obtained by abstracting one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, which is used in applications such as the above, and which have a predetermined number of carbon atoms. The methylene group of the alkylene group may be substituted with an oxygen atom.

[0080] In the present invention, L 1 However, it is preferable that the alkylene group has 1 to 5 carbon atoms, and more preferably that it is an alkylene group having 1 to 3 carbon atoms, and more preferably that it is an alkylene group having 1 to 2 carbon atoms, and more preferably that it is a methylene group. The above composition can form a cured product with excellent heat resistance and exhibits excellent curability.

[0081] In the above general formula (X), R B1 As an alkyl group having 1 to 10 carbon atoms represented by the above section "A1. Alicyclic epoxy compounds", R 1 Examples of alkyl groups having 1 to 20 carbon atoms used in the above include those that have a predetermined number of carbon atoms. Examples of substituents that substitute for the alkyl group include alkoxy groups, acryloyl groups, methacryloyl groups, and acetoxy groups.

[0082] In the present invention, n1 is preferably 2 to 8, more preferably 3 to 7, and particularly preferably 4 to 6. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability. Furthermore, in the present invention, R B1 However, it is preferable that the alkyl group has 1 to 5 carbon atoms, and more preferably that it has 2 to 4 carbon atoms, and in particular preferably that it has 2 to 3 carbon atoms. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0083] In the present invention, it is preferable that component (B) is a compound represented by the following general formula (B2). This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0084] [ka]

[0085] In formula (B2), n2 represents a number between 1 and 10 (inclusive).

[0086] In the present invention, n2 is preferably between 2 and 8, more preferably between 3 and 7, and particularly preferably between 4 and 6. By setting n2 within the above numerical range, the composition can form a cured product with excellent heat resistance and thus excellent curability.

[0087] In the present invention, the molecular weight of component (B) is preferably 600 or more and 4,500 or less, more preferably 1,000 or more and 3,500 or less, particularly preferably 1,400 or more and 3,100 or less, and most preferably 1,800 or more and 2,700 or less. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0088] In the present invention, the number of carbon atoms in component (B) is preferably 20 to 160, more preferably 36 to 110, more preferably 48 to 96, and more preferably 60 to 85. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0089] The content of component (B) is preferably 10 parts by mass or more and 75 parts by mass or less in a total of 100 parts by mass of components (A), (B), and (C), more preferably 20 parts by mass or more and 70 parts by mass or less, and particularly preferably 30 parts by mass or more and 60 parts by mass or less. By setting the numerical range as described above, the above composition can form a cured product with excellent heat resistance and thus excellent curability.

[0090] The content of component (B) above is preferably 10 parts by mass or more and 75 parts by mass or less per 100 parts by mass of solid content of the above composition, more preferably 20 parts by mass or more and 70 parts by mass or less, and particularly preferably 30 parts by mass or more and 60 parts by mass or less. By setting the numerical range above, the above composition can form a cured product with excellent heat resistance and thus excellent curability.

[0091] A3. Difunctional oxetane compounds and / or monofunctional oxetane compounds The composition of the present invention comprises a difunctional oxetane compound and / or a monofunctional oxetane compound as component (C). The above-mentioned difunctional oxetane compound refers to a compound having two oxetanyl groups as functional groups in its molecule. The above-mentioned monofunctional oxetane compound refers to a compound having one oxetanyl group as a functional group in its molecule. The above-mentioned difunctional oxetane compounds and monofunctional oxetane compounds may have functional groups other than the oxetanyl group. The functional groups other than the oxetanyl group may be the same as those described in section "A2. Trifunctional or more functional oxetane compounds". However, component (C) does not include those corresponding to component (A) above.

[0092] Specific examples of the above-mentioned difunctional oxetane compounds include, for example, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, and 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, which are alkanes to which two groups having oxetanyl groups are bonded. Examples of bisoxetane compounds include: compounds in which two groups having oxetanyl groups are bonded to a benzene ring, such as 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene and xylylenebisoxetane; and bisoxetane compounds such as ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, and tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether.

[0093] Specific examples of the above monofunctional oxetane compounds include, for example, 3-alkyl-3-(aryloxy)oxetanes such as 3-ethyl-3-[(phenoxy)methyl]oxetane; 3-alkyl-3-(oxyalkyl)oxetanes such as 3-ethyl-3-(hexyloxymethyl)oxetane and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane; 3-alkyl-3-(hydroxyalkyl)oxetanes such as 3-ethyl-3-(hydroxymethyl)oxetane; and 3-alkyl-3-(alkyl halogenated)oxetanes such as 3-ethyl-3-(chloromethyl)oxetane.

[0094] In the present invention, component (C) is preferably a monofunctional oxetane compound, and more preferably 3-alkyl-3-(oxyalkyl)oxetane or 3-alkyl-3-(aryloxy)oxetane, and particularly preferably 3-alkyl-3-(oxyalkyl)oxetane. This is because the above composition can form a cured product with excellent heat resistance and has excellent curability.

[0095] The above component (C) is preferably a compound having 5 to 30 carbon atoms, more preferably a compound having 8 to 20 carbon atoms, and particularly preferably a compound having 10 to 15 carbon atoms. This is because the above composition readily forms a cured product with excellent heat resistance.

[0096] The content of component (C) is preferably 5 parts by mass or more and 60 parts by mass or less in a total of 100 parts by mass of components (A), (B), and (C), more preferably 15 parts by mass or more and 55 parts by mass or less, and particularly preferably 20 parts by mass or more and 50 parts by mass or less. By setting the numerical range as described above, the above composition can form a cured product with excellent heat resistance and thus excellent curability.

[0097] The content of component (C) above is preferably 1 part by mass or more and 60 parts by mass or less per 100 parts by mass of solid content of the above composition, more preferably 15 parts by mass or more and 55 parts by mass or less, and particularly preferably 20 parts by mass or more and 50 parts by mass or less. By setting the numerical range above, the above composition can form a cured product with excellent heat resistance and thus excellent curability.

[0098] A4. Polymerization initiator The composition of the present invention may contain a polymerization initiator as component (D). It is preferable to use a photopolymerization initiator, and among these, a photocationic polymerization initiator, because it improves the curing reaction of the above composition. The above polymerization initiators may be used alone or in combination of two or more. Furthermore, if necessary, other polymerization initiators such as thermal cationic polymerization initiators, anionic polymerization initiators, and thermal latent curing agents may be included in addition to the above photopolymerization initiators.

[0099] (1) Photocationic polymerization initiator Photocatalytic polymerization initiators, also known as photoacid generators, are substances that generate acids capable of initiating cationic polymerization when irradiated with energy rays such as ultraviolet light. Specific examples of the above photocationic polymerization initiators include, for example, a cation moiety that is an aromatic sulfonium salt, aromatic iodonium salt, aromatic diazonium salt, aromatic ammonium salt, thianthrenium salt, thiooxantonium salt, or (2,4-cyclopentadiene-1-yl)[(1-methylethylbenzene]-Fe cation, and an anion moiety that is BF4 - PF6 - SbF6 - [BX4] - Examples include using an onium salt alone or in combination of two or more onium salts (where X is a phenyl group substituted with at least two fluorine or trifluoromethyl groups).

[0100] Specific examples of the above aromatic sulfonium salts include, for example, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, and diphenyl-4-(phenylthio)phenylsulfonium tetrakis(pentafluorophenyl)borate. Examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebishexafluorophosphate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebishexafluoroantimonate, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidebistetrafluoroborate, and bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl]sulfidetetrakis(pentafluorophenyl)borate.

[0101] Specific examples of the above aromatic iodonium salts include, for example, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrafluoroborate, and 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate.

[0102] Specific examples of the above aromatic diazonium salts include, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis(pentafluorophenyl)borate.

[0103] Specific examples of the above aromatic ammonium salts include, for example, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis(pentafluorophenyl)borate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluorophosphate, 1-(naphthylmethyl)-2-cyanopyridinium hexafluoroantimonate, 1-(naphthylmethyl)-2-cyanopyridinium tetrafluoroborate, and 1-(naphthylmethyl)-2-cyanopyridinium tetrakis(pentafluorophenyl)borate.

[0104] Specific examples of the above-mentioned thianthrenium salts include, for example, 5-methylthianthrenium hexafluorophosphate, 5-methyl-10-oxothianthrenium tetrafluoroborate, and 5-methyl-10,10-dioxothianthrenium hexafluorophosphate.

[0105] Specific examples of the thiooxantonium salts mentioned above include, for example, S-biphenyl 2-isopropylthiooxantonium hexafluorophosphate.

[0106] Other cationic moieties include, for example, (2,4-cyclopentadiene-1-yl)[(1-methylethylbenzene]-Fe salts such as (2,4-cyclopentadiene-1-yl)[(1-methylethylbenzene]-Fe(II) hexafluorophosphate, (2,4-cyclopentadiene-1-yl)[(1-methylethylbenzene]-Fe(II) hexafluoroantimonate, (2,4-cyclopentadiene-1-yl)[(1-methylethylbenzene]-Fe(II) tetrafluoroborate, and (2,4-cyclopentadiene-1-yl)[(1-methylethylbenzene]-Fe(II) tetrakis(pentafluorophenyl)borate.

[0107] Examples of commercially available photocationic polymerization initiators include CPI(R)-100P, CPI(R)-110P, CPI(R)-101A, CPI(R)-200K, CPI(R)-210S (all manufactured by Sunapro Co., Ltd.); Cyracure(R) Photocuring Initiator UVI-6990, Cyracure(R) Photocuring Initiator UVI-6992, Cyracure(R) Photocuring Initiator UVI-6976 (all manufactured by Dow Chemical Japan Ltd.); Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172, Adeka Optomer SP-300 (all manufactured by ADE Inc.) Examples include: KA brand; CI-5102, CI-2855 (both manufactured by Nippon Soda Co., Ltd.); Sun-Aid(R) SI-60L, Sun-Aid(R) SI-80L, Sun-Aid(R) SI-100L, Sun-Aid(R) SI-110L, Sun-Aid(R) SI-180L, Sun-Aid(R) SI-110, Sun-Aid(R) SI-180 (all manufactured by Sanshin Chemical Industry Co., Ltd.); EsaCure(R) 1064, EsaCure(R) 1187 (both manufactured by Lamberti); OmniCat 550, OmniCat 250 (manufactured by IGM Resin Co., Ltd.); and RhodeSill Photoinitiator 2074 (manufactured by Rhodia Japan Co., Ltd.).

[0108] The content of the above-mentioned photocationic polymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the solid content of the above composition, more preferably 0.5 parts by mass or more and 10 parts by mass or less, and particularly preferably 1 part by mass or more and 5 parts by mass or less. This is because the curing reaction of the above composition is more easily promoted by keeping the value within the above range.

[0109] (2) Thermal cationic polymerization initiator A thermal cationic polymerization initiator is a compound containing cationic species that is excited by heating, and acts as a polymerization initiator that promotes thermal curing through a thermal decomposition reaction. It is also called a thermal acid generator. Examples of the above-mentioned thermal cationic polymerization initiators include honate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, bis(cyclohexylsulfonyl)diazomethane, bis(tert-butylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, triphenylsulfonium trifluoromethanesulfonate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4,6-trimethylphenylsulfonium-p-toluenesulfonate, and diphenyl-p-phenylthiophenylsulfonium hexafluorophosphate.

[0110] Examples of commercially available thermal cationic polymerization initiators include the diazonium salt-based AMERICURE series (manufactured by American Scan Corporation); the iodonium salt-based UVE series (manufactured by General Electric Corporation); the FC series (manufactured by 3M Corporation); UV9310C (manufactured by GE Toshiba Silicone Corporation); the WPI series and WPAG series (manufactured by Fujifilm Wako Pure Chemical Corporation); the sulfonium salt-based CYRACURE series (manufactured by Union Carbide Corporation); the UVI series (manufactured by General Electric Corporation); the CD series (manufactured by Sartomer Corporation); the Optomer SP series and Optomer CP series (manufactured by ADEKA Corporation); the San-Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.); the CI series (manufactured by Nippon Soda Co., Ltd.); and the CPI series (manufactured by Sunapro Corporation).

[0111] The content of the above-mentioned thermal cationic polymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the solid content of the above composition, and more preferably 0.1 parts by mass or more and 10 parts by mass or less. This is because the curing reaction of the above composition is more easily promoted by keeping the value within the above range.

[0112] (3) Anionic polymerization initiator If the composition of the present invention contains an anionic polymerizable compound as described later, it may also contain an anionic polymerization initiator. Examples of anionic polymerization initiators include photobase generators. The above-mentioned photobase generator refers to a compound that generates a base upon irradiation with energy rays such as ultraviolet light. In particular, it is preferable that the compound is a salt containing a borate anion because it has good sensitivity to light. Examples of commercially available photobase generators include U-CAT5002 (manufactured by Sunapro Co., Ltd.); P3B, BP3B, N3B, and MN3B (all manufactured by Showa Denko Corporation).

[0113] The content of the above-mentioned anionic polymerization initiator is preferably 0.1 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the solid content of the above composition, and more preferably 0.1 parts by mass or more and 10 parts by mass or less. This is because the curing reaction of the above composition is more easily promoted by keeping the content within the above numerical range.

[0114] (4) Latent curing agent Latent curing agents are those that undergo thermal curing upon heating, and examples include acid anhydride-based curing agents, amine-based curing agents, phenol-based curing agents, polyamide resins, and imidazole-based curing agents. Examples of the above-mentioned acid anhydride-based curing agents include methyltetrahydrophthalic anhydride (e.g., methyltetrahydrophthalic anhydride), methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.), dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, nadic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, 4-(4-methyl-3-pentenyl)tetrahydrophthalic anhydride, succinic anhydride, adipic anhydride, sebadic anhydride, dodecanediic anhydride, methylcyclohexenetetracarboxylic anhydride, vinyl ether-maleic anhydride copolymer, alkylstyrene-maleic anhydride copolymer, and the like.

[0115] Examples of the above amine-based curing agents include aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, and polypropylenetriamine; mensendiamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, diaminodicyclohexylmethane, bis(aminomethyl)cyclohexane, N-aminoethylpiperazine, and 3,9-bis(3-aminopropyl)-3,4. Examples include alicyclic polyamines such as 8,10-tetraoxaspiro[5,5]undecane; mononuclear polyamines such as m-phenylenediamine, p-phenylenediamine, torylene-2,4-diamine, torylene-2,6-diamine, mesitylene-2,4-diamine, 3,5-diethyltrylene-2,4-diamine, and 3,5-diethyltrylene-2,6-diamine; and aromatic polyamines such as biphenylenediamine, 4,4-diaminodiphenylmethane, 2,5-naphthylenediamine, and 2,6-naphthylenediamine.

[0116] Examples of the phenolic curing agents mentioned above include modified phenolic resins, aralkyl resins such as paraxylylene / metaxylylene modified phenolic resins, terpene modified phenolic resins, dicyclopentadiene modified phenolic resins, and triphenolpropane.

[0117] Examples of the polyamide resins mentioned above include polyamide resins having either a primary amino group or a secondary amino group, or both, within the molecule.

[0118] Examples of the imidazole-based curing agents mentioned above include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and 1-cyanoethyl Examples include -2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-methylimidazolium isocyanurate, 2-phenylimidazolium isocyanurate, 2,4-diamino-6-[2-methylimidazolyl-(1)]-ethyl-s-triazine, and 2,4-diamino-6-[2-ethyl-4-methylimidazolyl-(1)]-ethyl-s-triazine.

[0119] Examples of the polymercaptan-based curing agents mentioned above include polymercaptans and polysulfide resins, and those that are liquid at room temperature are preferred. This is because they allow for a good curing reaction of the composition.

[0120] Examples of the polycarboxylic acids mentioned above include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, and carboxyl group-containing polyesters.

[0121] The content of the latent curing agent is preferably 0.1 parts by mass or more and 75 parts by mass or less, and more preferably 5 parts by mass or more and 30 parts by mass or less, in a total of 100 parts by mass of components (A), (B), and (C). This is because the curing reaction of the composition is more easily promoted by keeping the content within the above numerical range.

[0122] A5. Other polymerizable components The composition of the present invention may include, in addition to the above-mentioned components (A), (B), and (C), and optionally component (D), other polymerizable components to adjust the physical properties of the cured product of the composition. Other polymerizable components include, for example, aromatic epoxy compounds and aliphatic epoxy compounds.

[0123] (1) Aromatic epoxy compounds The above-mentioned aromatic epoxy compound refers to an epoxy compound that contains an aromatic ring but does not contain an oxetanyl group or an alicyclic epoxy group. The above-mentioned aromatic ring is not particularly limited as long as it is an aromatic ring, and examples include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, etc. In the present invention, it is preferable that the aromatic ring is a benzene ring, because the cured product of the above composition has a high glass transition temperature.

[0124] Examples of the above aromatic epoxy compounds include monovalent phenols such as phenol, cresol, and butylphenol, or glycidyl ethers of their alkylene oxide adducts; polyglycidyl ethers of polyvalent phenols having at least one aromatic ring, or their alkylene oxide adducts; phenol novolac type epoxy compounds; glycidyl ethers of phenols 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; polyglycidyl esters of polybasic acid aromatic compounds having two or more carboxylic acids, such as phthalic acid, terephthalic acid, and trimellitic acid; glycidyl esters of benzoic acids such as benzoic acid, toluic acid, and naphthoic acid; and epoxides of styrene oxide or divinylbenzene.

[0125] In the present invention, the aromatic epoxy compound is preferably a polyglycidyl ether of an aromatic compound having two or more alcoholic hydroxyl groups, and more preferably a glycidyl ether of bisphenol A, bisphenol E, or bisphenol F, and particularly preferably a glycidyl ether of bisphenol A. This is because the above structure results in a high glass transition temperature for the cured product of the composition of the present invention.

[0126] The amount of the above aromatic epoxy compound may be such that the composition of the present invention can form a cured product with excellent heat resistance and has excellent curability. In the composition of the present invention, if the above-mentioned aromatic epoxy compound is included, the content of the aromatic epoxy compound is preferably 0.1 parts by mass or more and 80 parts by mass or less, out of 100 parts by mass of the total of the alicyclic epoxy compound, aromatic epoxy compound and aliphatic epoxy compound of component (A), more preferably 5 parts by mass or more and 75 parts by mass or less, and particularly preferably 10 parts by mass or more and 70 parts by mass or less. This is because the curing reaction of the above-mentioned composition is more easily promoted by keeping the numerical range as described above.

[0127] (2) Aliphatic epoxy compounds The above aliphatic epoxy compounds refer to epoxy compounds that have an epoxy group and do not contain aromatic rings, oxetanyl groups, or alicyclic epoxy groups. Specific examples of the above aliphatic epoxy compounds include, for example, polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts; polyglycidyl esters of aliphatic long-chain polybasic acids; homopolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate; copolymers synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate with other vinyl monomers; Glycidyl ethers of polyhydric alcohols, such as diglycidyl ethers of diols, triglycidyl ethers of glycerin, triglycidyl ethers of trimethylolpropane, tetraglycidyl ethers of sorbitol, and hexaglycidyl ethers of dipentaerythritol; Examples include polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as propylene glycol, trimethylolpropane, and glycerin, and diglycidyl esters of aliphatic long-chain dibasic acids. Furthermore, examples include monoglycidyl ethers of aliphatic higher alcohols, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides thereto, glycidyl esters of higher fatty acids, epoxidized soybean oil, octyl epoxystearate, butyl epoxystearate, and epoxidized polybutadiene.

[0128] In the present invention, the aliphatic epoxy compound is preferably a diglycidyl ether of a diol, and among these, a diglycidyl ether of a diol with a molecular weight of 80 to 200 is preferred, and particularly a diglycidyl ether of a diol with a molecular weight of 90 to 150 is preferred. This is because the curing reaction of the above composition is more easily accelerated by using the above numerical range.

[0129] Examples of commercially available aliphatic epoxy compounds include those described in International Publication No. 2019 / 177134 and Japanese Patent No. 6103653.

[0130] The content of the above-mentioned aliphatic epoxy compound may vary as long as the composition of the present invention can form a cured product with excellent curability and a high glass transition temperature. In the composition of the present invention, if an aliphatic epoxy compound is included, the content of the aliphatic epoxy compound is preferably 0.1 parts by mass or more and 80 parts by mass or less, out of 100 parts by mass of the total of the alicyclic epoxy compound (A), aromatic epoxy compound and aliphatic epoxy compound, and more preferably 5 parts by mass or more and 75 parts by mass or less, and particularly preferably 10 parts by mass or more and 70 parts by mass or less. This is because the curing reaction of the composition is more easily promoted by keeping the content within the above numerical range.

[0131] A6. solvent The compositions of the present invention may contain a minimum amount of solvent to disperse or dissolve each component of the composition. Preferably, the above solvent is liquid at room temperature (25°C) and atmospheric pressure and does not react with components (A), (B), (C), (D) and other polymerizable components. Therefore, even if they are liquid at room temperature (25°C) and atmospheric pressure, the alicyclic epoxy compounds described in section "A1. Alicyclic epoxy compounds," the trifunctional or more oxetane compounds described in section "A2. Trifunctional or more oxetane compounds," the difunctional oxetane compounds and / or monofunctional oxetane compounds described in section "A3. Difunctional oxetane compounds and / or monofunctional oxetane compounds," the polymerization initiators described in section "A4. Polymerization initiators," the aromatic epoxy compounds and aliphatic epoxy compounds described in section "A5. Other polymerizable components," etc., are not included in the solvent, even if they are liquid at room temperature (25°C) and atmospheric pressure.

[0132] Either water or an organic solvent can be used as such a solvent, but an organic solvent is preferred.

[0133] The above organic solvents include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, and 2-heptanone; ether solvents such as ethyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol; cellosolve solvents such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol, and diacetone alcohol; ethylene glycol monomethyl acetate, ethylene glycol monoethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), and dipropylene glycol monomethyl ether Ether ester solvents such as cete, 3-methoxybutyl acetate, ethoxyethyl propionate, 1-t-butoxy-2-propanol, and cyclohexanol acetate; aromatic solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as hexane, heptane, octane, and cyclohexane; terpene hydrocarbon oils such as turpentine, D-limonene, and pinene; paraffinic solvents such as mineral spirits, Swazole #310 (Cosmo Matsuyama Petroleum Co., Ltd.), and Solvesso #100 (Exxon Chemicals, Inc.); tetrachlorides Examples of solvents include halogenated aliphatic hydrocarbon solvents such as carbon dioxide, chloroform, trichloroethylene, methylene chloride, and 1,2-dichloroethane; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and water. These solvents may be used individually or in combination of two or more to form a mixed solvent. Among the aforementioned organic solvents, ketones, alcohol-based solvents, ether ester-based solvents, or aromatic solvents are preferred, and ketones or aromatic solvents are more preferred. This is because the above composition facilitates the formation of a cured product with excellent heat resistance.

[0134] The amount of the solvent mentioned above is not particularly limited, as long as the composition can form a cured product with excellent heat resistance and excellent curability. For example, it is preferably 1,000 parts by mass or less per 100 parts by mass of solid content of the composition, more preferably 500 parts by mass or less, particularly preferably 100 parts by mass or less, and most preferably not contained at all. This is because by setting the amount within the above numerical range, the composition can form a cured product with high heat resistance and excellent curability.

[0135] A7. Composition The method for producing the above composition is not particularly limited as long as it can uniformly mix each of the above components. For example, a method can be used in which component (A), component (B), component (C), and other components such as component (D) as needed are added and mixed. As for the mixing method, a known mixing apparatus can be used, for example, a method using a three-roll mill, a sand mill, a ball mill, etc.

[0136] The applications of the above composition are not particularly limited as long as a balance between electrical properties and adhesive strength is required. Examples include adhesives, resist materials for printed circuit boards, resist inks, pigment resist inks for car filters, semiconductor encapsulants, inks, plastic paints, paper printing, film coatings, glass coatings, shatterproof paints, furniture coatings, FRP, linings, and in the field of electronics, insulating varnishes, insulating sheets, laminates, plasma display panels, display elements and other display media, optical anisotropies such as phase difference plates, polarizers, optical polarizing prisms, and various optical filters, adhesives, insulating materials, structural materials, and optical waveguide cladding.

[0137] In the present invention, it is preferable that the above uses are various coating materials such as adhesive materials, film coatings, glass coatings, anti-scattering paints, furniture coatings, etc. This is because a cured product having a high glass transition temperature and the effects of a composition excellent in curability can be effectively exhibited.

[0138] B. Cured Product Next, the cured product of the present invention will be described. The cured product of the present invention is a cured product of the above composition of the present invention.

[0139] According to the present invention, since the above composition is used, a cured product having a high glass transition temperature can be formed, and a composition excellent in curability can be provided. Note that since the composition of the present invention is the same as the content described in the section of "A. Composition" above, the description here is omitted.

[0140] Regarding the uses and the like of the cured product of the present invention, they can be the same as the content described in the section of "A. Composition" above.

[0141] The method for producing the cured product of the present invention is not particularly limited as long as it is a method capable of forming the cured product of the above composition into a desired shape. For example, a step of curing the above composition can be mentioned.

[0142] According to the present invention, since the above composition is used, a cured product having a high glass transition temperature can be easily formed.

[0143] 1. Curing Step The above curing step is a step of curing the above composition. The method for curing the above composition is not particularly limited as long as it is a method capable of polymerizing the component (A), the component (B), and the component (C). Examples thereof include a method of irradiating light (energy rays) to the coating film of the above composition. This is because the polymerization of the component (A), the component (B), and the component (C) is easy.

[0144] In this process, as the light source of the energy rays used for the polymerization of the above components (A), (B) and (C), electromagnetic wave energy having a wavelength of 2,000 Å or more and 7,000 Å or less obtained from an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury vapor arc lamp, a xenon arc lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an excimer lamp, a germicidal lamp, a light emitting diode, a CRT light source, etc., or high energy rays such as electron beams, X-rays, and radiation can be used. Preferably, an ultra-high pressure mercury lamp, a mercury vapor arc lamp, a carbon arc lamp, a xenon arc lamp, a light emitting diode, etc. that emit light with a wavelength of 300 nm or more and 450 nm or less are used. This is because the polymerization of the above components (A), (B) and (C) is easy.

[0145] There is no particular limitation on the irradiation amount of the energy rays, and it can be appropriately determined according to the composition of the composition. From the viewpoint of preventing deterioration of the components in the composition, the irradiation amount is preferably 100 mJ / cm 2 or more and 2,000 mJ / cm 2 or less at 365 nm.

[0146] In this process, it is preferable that the above curing method is a method of using both a method of irradiating energy rays and a method of heating, and more specifically, it is preferable to perform the method of irradiating energy rays and the method of heating in this order. This is because the polymerization of the above components (A), (B) and (C) can proceed efficiently.

[0147] 2. Other processes The above production method may have other processes as necessary. Examples of such processes include a process of applying the above composition to a substrate before the process of curing the composition. As the method of applying the above composition, known methods such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various printing methods, and dipping can be used.

[0148] The above-mentioned substrate can be appropriately set according to the intended use of the cured product, and examples include soda glass, quartz glass, semiconductor substrates, metals, paper, plastics, and the like. Furthermore, the cured product may be used either after being formed on the substrate and then peeled off from the substrate, or transferred from the substrate to another adherend.

[0149] The above manufacturing method may include a step of applying the composition to a substrate to form a coating film, and then heating the coating film. Methods for heating the coating film of the composition in this step include using a hot plate or other heating plate, or using an atmospheric oven, inert gas oven, vacuum oven, hot air circulation oven, etc.

[0150] The heating temperature when heating the coating film is not particularly limited, but from the viewpoint of facilitating polymerization of components (A), (B), and (C) above, it is preferably 70°C to 200°C, and more preferably 90°C to 150°C. The heating time when heating the coating film is not particularly limited, but from the viewpoint of improving productivity, it is preferably between 1 minute and 60 minutes, and more preferably between 1 minute and 30 minutes.

[0151] C. Others The present invention includes the following embodiments. [1] A composition containing the following components (A), (B), and (C). (A) Component: Alicyclic epoxy compound (B) Component: Trifunctional or higher oxetane compound (C) Component: Difunctional oxetane compound and / or monofunctional oxetane compound

[0152] [2] The composition according to [1], wherein the alicyclic epoxy compound comprises at least one compound represented by the following general formulas (A-1), (A-2), (A-3), (A-4), and (A-5).

[0153] [ka]

[0154] In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0155] [ka]

[0156] In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0157] [ka]

[0158] In formula (A-3), R 31 , R 32 , R 33 , R 34 , R 35 , R36 , 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 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0159]

Chemical formula

[0160] In 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 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.

[0161]

Chemical formula

[0162] In formula (A-5), R 71 , R 72 , R 73 , R 74 , R 75 , R 76 , R 77 , R 78 , R79 , R 80 , R 81 , R 82 , R 83 , R 84 , R 85 , R 86 , R 87 and R 88 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Z represents a single bond, an alkylene group with 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group consisting of multiple such bonds.

[0163] [3] The composition according to [1] or [2], wherein the above component (B) is a compound represented by the following general formula (B1).

[0164] [ka]

[0165] In formula (B1), X represents an oxetanyl group represented by the following general formula (X), n1 represents a number between 1 and 10 (inclusive).

[0166] [ka]

[0167] In equation (X), * represents the bond position between X and an adjacent oxygen atom. R B1 This represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and the alkyl group may have further substituents.

[0168] [4] The composition according to any one of [1] to [3], wherein the content of component (A) is 0.5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the solid content of the composition.

[0169] [5] The composition according to any one of [1] to [4], wherein the content of component (B) is 10 parts by mass or more and 75 parts by mass or less per 100 parts by mass of the solid content of the composition.

[0170] [6] The composition according to any one of [1] to [5], wherein the content of component (C) is 5 parts by mass or more and 60 parts by mass or less per 100 parts by mass of the solid content of the composition.

[0171] [7] A cured product of any one of the compositions described in [1] to [6].

[0172] The present invention is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of the present invention and achieves similar effects is included within the technical scope of the present invention. [Examples]

[0173] The present invention will be described in more detail below with specific examples of the compositions of the present invention, but the present invention is not limited to these examples.

[0174] [Examples 1 to 32 and Comparative Examples 1 to 7] The compositions were prepared by blending each component according to Tables 1 to 5 below. The following materials were used for each component. Note that the amounts in the tables represent parts by mass of each component.

[0175] (A) Component: Alicyclic epoxy compound A1: Celoxide (registered trademark) 2021P (Daicel Corporation product, CAS No. 2386-87-0, compound represented by the above formula (A-5), molecular weight: 252.2, epoxy equivalent: 126.1 g / eq.) A2: Epocalic (registered trademark) THI-DE (ENEOS Corporation product, CAS No. 2886-89-7, compound represented by the above formula (A-1), molecular weight: 152.19, epoxy equivalent: 76.09 g / eq.)

[0176] (B) Component: Trifunctional or higher oxetane compound B1: Aronoxetane (registered trademark) OXT-191 (a product of Toagosei Co., Ltd., a compound in which the average of n2 in the above formula (B2) is 5)

[0177] (C) Component: Difunctional oxetane compound and / or monofunctional oxetane compound C1: Aronoxetane (registered trademark) OXT-211 (product of Toagosei Co., Ltd., CAS No. 3897-65-2, monofunctional oxetane compound) C2: Aronoxetane (registered trademark) OXT-212 (product of Toagosei Co., Ltd., CAS No. 298695-60-0, monofunctional oxetane compound)

[0178] (D) Component: Polymerization initiator D1-1: A 50% by mass propylene carbonate solution containing the compound represented by the following formula (D1a) and the compound represented by the following formula (D1b) in a mass ratio of 1:1.

[0179] [ka]

[0180] (E) Component: Other compounds E1: Bisphenol A diglycidyl ether (aromatic epoxy compound) E2: Neopentyl glycol diglycidyl ether (aliphatic epoxy compound)

[0181] For each of the obtained compositions, the immediate curing properties, deep curing properties, reaction rate during exposure, and cured product Tg were evaluated according to the following procedure. The results are shown in Tables 1 to 5.

[0182] 1. Instant curing The immediate curing properties were evaluated using the compositions of Examples 1 to 32 and Comparative Examples 1 to 7. Each composition is applied to a 60 μm thick TAC film to form a coating film with a thickness of 1 mm, and ultraviolet light (365 nm) is applied using a high-pressure mercury lamp at 100 mW and 1,400 mJ / cm². 2The coating was cured by irradiation under the specified exposure conditions to obtain a cured product. After curing, the surface of the cured product was examined by touch at various points in time and evaluated according to the following criteria. Furthermore, a rating of ++ or + is preferred for the immediate curing properties, with ++ being particularly preferred. This is because compositions with high immediate curing properties exhibit excellent curing capabilities. <Evaluation Criteria> ++: Became tack-free within 20 seconds after exposure. +: Became tuck-free between 20 and 60 seconds after exposure. -: The film did not become tack-free even after 60 seconds had passed since exposure.

[0183] 2. Deep hardening Each composition was filled into a 3mm pore tube, and ultraviolet light (365nm) was applied from one end of the tube using a high-pressure mercury lamp at 100mW and 1,400mJ / cm². 2 The material was irradiated under the specified exposure conditions. The resulting cured material was removed from the tube, the distance from the exposed surface to the tip of the cured material was measured, and it was evaluated according to the following criteria. Furthermore, a deep curing performance rating of ++ or + is preferred, with ++ being particularly preferred. This is because compositions with high deep curing performance exhibit excellent curing properties. <Evaluation Criteria> ++: 1mm or more +: 0.5mm or more and less than 1mm -: Less than 0.5mm

[0184] 3. Response rate during exposure (%) Each composition was applied to a 60 μm thick TAC film to form a coating film with a thickness of 1 mm. A light irradiation device (DSC7000, manufactured by Hitachi High-Tech Science Co., Ltd.) was used to irradiate the film with ultraviolet light (365 nm) at a rate of 1,400 mJ / cm². 2 After irradiation, an additional 10,000 mJ / cm² is administered. 2 Irradiation was performed at 1,400 mJ / cm². 2 Heat output after irradiation and 10,000 mJ / cm² 2 The amount of heat after irradiation was measured, and the reaction rate during exposure was calculated using the following formula and evaluated according to the following criteria. Reaction rate during exposure = [1,400 mJ / cm²] 2[Heat after irradiation] / ([Heat after irradiation of 1,400 mJ / cm²] + [10,000 mJ / cm²] 2 (Heat output after irradiation) × 100 Furthermore, the reaction rate during exposure should preferably be ++ or +, and ++ is particularly preferred. This is because compositions with a high reaction rate during exposure exhibit excellent curability. <Evaluation Criteria> ++: Exposure response rate of 90% or higher +: Response rate at exposure is 85% or higher but less than 90% -: Reaction rate during exposure is less than 85%

[0185] 4. Cured product Tg (℃) Each composition is applied to a polyethylene terephthalate (PET) film using a bar coater method to form a coating film with a cured film thickness of 1 mm, and ultraviolet light (365 nm) is applied using a high-pressure mercury lamp at 100 mW and 1,400 mJ / cm². 2 The coating film was cured by irradiation under the specified exposure conditions to obtain a cured product. The cured product was removed, and its glass transition temperature (Tg) was measured using a viscoelasticity measuring device (DMA7100) manufactured by Hitachi High-Tech Science Co., Ltd., and evaluated according to the following criteria. Furthermore, a cured product Tg of ++ or + is preferred, and ++ is particularly preferred. This is because compositions with a high cured product Tg exhibit excellent heat resistance. <Evaluation Criteria> ++: Tg is 200℃ or higher +: Tg is between 150°C and 200°C -:Tg is less than 150℃

[0186] [Table 1]

[0187] [Table 2]

[0188] [Table 3]

[0189] [Table 4]

[0190] [Table 5]

[0191] From Tables 1 to 5 above, it was confirmed that the compositions of the present invention exhibit excellent curability, as they have good immediate curability, deep curability, and reaction rate during exposure. Furthermore, the cured products of the compositions of the present invention have excellent heat resistance due to their high glass transition temperature.

Claims

1. A composition containing the following components (A), (B), and (C): (A) Component: Alicyclic epoxy compound (B) Component: Trifunctional or higher oxetane compound (C) Component: Monofunctional oxetane compound The alicyclic epoxy compound comprises at least one compound selected from those represented by the following general formulas (A-1), (A-2), (A-3), (A-4), and (A-5), The content of component (B) is 10 parts by mass or more and 75 parts by mass or less per 100 parts by mass of the solid content of the composition. A composition that does not contain a difunctional oxetane compound. 【Chemistry 1】 (In 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 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.) 【Chemistry 2】 (In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. 【Transformation 3】 (In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. 【Chemistry 4】 (In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. 【Transformation 5】 (In 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 of these independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms. Z represents a single bond, an alkylene group with 1 to 4 carbon atoms, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, or a group consisting of multiple such bonds.

2. The composition according to claim 1, wherein the above-mentioned component (B) is a compound represented by the following general formula (B1). 【Transformation 6】 (In formula (B1), X represents an oxetanyl group represented by the following general formula (X), n1 represents a number between 1 and 10 (inclusive). 【Transformation 7】 (In formula (X), * represents the bond position between X and an adjacent oxygen atom.) L １ This represents an alkylene group having 1 to 10 carbon atoms, and some of the methylene groups of the alkylene group may be substituted with oxygen atoms. R Ｂ１ (wherein represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, the alkyl group may further have substituents.)

3. The composition according to claim 1, wherein the content of component (A) is 0.5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the solid content of the composition.

4. The composition according to claim 1, wherein the content of component (C) is 1 part by mass or more and 60 parts by mass or less per 100 parts by mass of the solid content of the composition.

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

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