Composition comprising compound having polyoxyalkylene chain

Abstract

To improve the elongation at break of a cured product of a composition while enhancing the handleability of the composition.SOLUTION: A composition comprising a compound represented by the following formula (1) [in formula (1), R11 and R12 each independently represent a hydrogen atom or a methyl group, and R13 represents a divalent group having a polyoxyalkylene chain], wherein the polyoxyalkylene chain contains 100 or more oxyalkylene groups.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a composition containing a compound having a polyoxyalkylene chain.

Background Art

[0002] In electronic components and the like that generate heat during use, a thermally conductive material (sometimes called a heat dissipating material) called a thermal interface material (TIM) is used to efficiently dissipate heat. The TIM contains, for example, a polymer and a thermally conductive filler.

[0003] As described above, a polymer suitable for the use (application target) of the TIM is selected. Specifically, for example, a composition containing a polymer may be required to have low viscosity and excellent handleability, and the cured product of the composition may be required to have low elasticity. On the other hand, for example, Patent Document 1 discloses a curable silicone composition that has good handling workability and forms a cured product with a low elastic modulus.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] According to the studies of the present inventors, in a cured product of a composition in which handleability is improved by using a low-viscosity polymer, it may be required to increase the elongation at break. However, it is not always easy to achieve these simultaneously.

[0006] Therefore, an object of the present invention is to improve the handleability of the composition while improving the elongation at break of the cured product of the composition.

Means for Solving the Problems

[0007] As a result of intensive research, the inventors have found that a composition containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups can form a cured product having a high elongation at break while having a low viscosity and excellent handleability. The present invention provides the following [1] to [7] in several aspects.

[0008] [1] Containing a compound represented by the following formula (1), [Chemical formula] [In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, and R 13 represents a divalent group having a polyoxyalkylene chain.] A composition in which the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more. [2] The composition according to [1], wherein the polyoxyalkylene chain contains an oxyethylene group. [3] The composition according to [1], wherein the polyoxyalkylene chain contains an oxypropylene group. [4] The composition according to [1], wherein the polyoxyalkylene chain is a copolymer chain containing an oxyethylene group and an oxypropylene group. [5] The composition according to [4], wherein the copolymer chain is a random copolymer chain. [6] The composition according to any one of [1] to [5], wherein the weight average molecular weight of the compound represented by formula (1) is 5000 or more. [7] The composition according to any one of [1] to [6], wherein the viscosity of the compound represented by formula (1) at 25°C is 200 Pa·s or less. [Advantages of the Invention]

[0009] According to the present invention, it is possible to improve the handleability of the composition and improve the elongation at break of the cured product of the composition. [Embodiments for Carrying Out the Invention]

[0010] Hereinafter, embodiments of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments.

[0011] In this specification, "(meth)acryloyl" means "acryloyl" and the corresponding "methacryloyl", and the same applies to similar expressions such as "(meth)acrylate" and "(meth)acrylic".

[0012] The weight average molecular weight (Mw) in this specification is measured under the following conditions using gel permeation chromatography (GPC), and means a value determined using polystyrene as a standard substance. · Measuring instrument: HLC-8320GPC (product name, manufactured by Tosoh Corporation) · Analytical column: TSKgel SuperMultipore HZ-H (connected in three) (product name, manufactured by Tosoh Corporation) · Guard column: TSKguardcolumn SuperMP(HZ)-H (product name, manufactured by Tosoh Corporation) · Eluent: THF · Measurement temperature: 25°C

[0013] One embodiment of the present invention is a composition containing a compound represented by the following formula (1).

Chemical formula

[0014] In one embodiment, one of R 11 and R 12 may be a hydrogen atom and the other may be a methyl group. In another embodiment, both of R 11 and R 12 may be hydrogen atoms. In another embodiment, R 11and R 12 Both may be methyl groups.

[0015] The number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more. The composition of the present embodiment has a structure represented by the formula (1) and contains a compound having 100 or more oxyalkylene groups in the polyoxyalkylene chain, so that a cured product having excellent elongation at break can be formed while having low viscosity and excellent handleability. Further, in one embodiment, the cured product of this composition can be low elastic and high strength. From these viewpoints, the number of oxyalkylene groups in the polyoxyalkylene chain is preferably 130 or more, 180 or more, 200 or more, 220 or more, 250 or more, 270 or more, 300 or more, or 320 or more. The number of oxyalkylene groups in the polyoxyalkylene chain may be 600 or less, 570 or less, or 530 or less.

[0016] In one embodiment, the polyoxyalkylene chain contains an oxyethylene group (in other words, a structural unit represented by the following formula (2)). Thereby, while further suppressing the increase in the viscosity of the composition, the strength of the cured product can be further increased.

Chemical formula

[0017] In this case, R 13 may be a divalent group having a polyoxyethylene chain, and the compound represented by the formula (1) is preferably a compound represented by the following formula (1-2) (polyethylene glycol di(meth)acrylate).

Chemical formula

[0018] In another embodiment, the polyoxyalkylene chain contains an oxypropylene group (in other words, a structural unit represented by the following formula (3)). Thereby, the handling of the composition can be made easier.

Chemical formula

[0019] In this case, R 13 may be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formula (1-3) (polypropylene glycol di(meth)acrylate).

Chemical formula

[0020] In another embodiment, from the viewpoint of further facilitating the handleability of the composition and the low elasticity, high elongation and high strength of the cured product, the polyoxyalkylene chain is preferably a copolymer chain containing an oxyethylene group and an oxypropylene group. The copolymer chain may be any of an alternating copolymer chain, a block copolymer chain, or a random copolymer chain. The copolymer chain is preferably a random copolymer chain from the viewpoint of further facilitating the handling of the composition.

[0021] In each of the above-described embodiments, in addition to the oxyethylene group and the oxypropylene group, the polyoxyalkylene chain may have an oxyalkylene group having 4 to 5 carbon atoms, such as an oxytetramethylene group, an oxybutylene group, or an oxypentylene group, as a structural unit.

[0022] R 13In addition to the polyoxyalkylene chain described above, it may be a divalent group further having other organic groups. The other organic groups may be chain-like groups other than the polyoxyalkylene chain. For example, they may be a methylene chain (a chain having -CH2- as a structural unit), a polyester chain (a chain containing -COO- in the structural unit), a polyurethane chain (a chain containing -OCON- in the structural unit), and the like.

[0023] For example, the compound represented by formula (1) may be a compound represented by the following formula (1-4).

Chemical formula

[0024] k1 and k3 can each independently take the same lower limit and upper limit as the number of the above-described oxyalkylene groups. k2 may be, for example, an integer of 16 or less.

[0025] A plurality of R 14 and R 15 may be the same as each other or different from each other. A plurality of R 14 and R 15 each preferably contain an ethylene group and a propylene group. That is, the polyoxyalkylene chain represented by (R 14 O) k1 and the polyoxyalkylene chain represented by (R 15 O) k3 are each preferably a copolymer chain containing an oxyethylene group and an oxypropylene group.

[0026] The weight average molecular weight of the compound represented by formula (1) is preferably 5000 or more, 6000 or more, 7000 or more, 8000 or more, 9000 or more, 10000 or more, 11000 or more, 12000 or more, 13000 or more, 14000 or more, or 15000 or more, from the viewpoint that the cured product has lower elasticity and excellent elongation. The weight average molecular weight of the compound represented by formula (1) is preferably 100000 or less, 80000 or less, 60000 or less, 40000 or less, or 30000 or less, from the viewpoint of making it easier to further adjust the viscosity of the composition.

[0027] The compound represented by formula (1) may be liquid at 25°C. In this case, the viscosity of the compound represented by formula (1) at 25°C is preferably 500 Pa·s or less, more preferably 350 Pa·s or less, still more preferably 300 Pa·s or less, and particularly preferably 200 Pa or less, from the viewpoint of further improving the handleability of the composition. The viscosity of the compound represented by formula (1) at 25°C may be 0.1 Pa·s or more, 0.2 Pa·s or more, or 0.3 Pa·s or more.

[0028] The compound represented by formula (1) may be solid at 25°C. In this case, from the viewpoint of further improving the handleability of the composition, the compound represented by formula (1) is preferably liquid at 50°C. Also, in this case, the viscosity of the compound represented by formula (1) at 50°C is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, still more preferably 30 Pa·s or less, and particularly preferably 20 Pa·s or less, from the viewpoint of further improving the handleability of the composition. The viscosity of the compound represented by formula (1) at 50°C may be 0.1 Pa·s or more, 0.2 Pa·s or more, or 0.3 Pa·s or more.

[0029] Viscosity means the value measured based on JIS Z 8803, and specifically means the value measured by an E-type viscometer (for example, PE-80L manufactured by Toki Sangyo Co., Ltd.). The calibration of the viscometer can be carried out based on JIS Z 8809-JS14000. The viscosity of the compound represented by formula (1) can be adjusted by adjusting the weight average molecular weight of the said compound.

[0030] The content of the compound represented by the formula (1) may be, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total amount of the composition, and may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less.

[0031] The composition may contain only the compound represented by the formula (1) as the polymerizable compound. The composition may further contain other polymerizable compounds (details will be described later) other than the compound represented by the formula (1). In this case, the content of the compound represented by the formula (1) may be, for example, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more, based on 100 parts by mass of the total of the compound represented by the formula (1) and other polymerizable compounds (hereinafter referred to as "the total content of the polymerizable components"), and may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.

[0032] The composition may further contain other polymerizable compounds copolymerizable with the compound represented by the above formula (1) for the purpose of adjusting the physical properties of the composition and the like.

[0033] Other polymerizable compounds may be, for example, compounds having one (meth)acryloyl group. The compound may be, for example, an alkyl (meth)acrylate. Other polymerizable compounds may be compounds having, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocycle, an alkoxy group, a phenoxy group, a group containing a silane group, a group containing a siloxane bond, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group. In particular, by containing an alkyl (meth)acrylate in the composition, the viscosity of the composition can be adjusted. Further, by containing a compound having a hydroxyl group, a carboxyl group, an amino group, or an epoxy group in addition to the (meth)acryloyl group in the composition, the adhesion of the composition and its cured product to the member can be further improved.

[0034] The alkyl group in the alkyl (meth)acrylate (the alkyl group portion other than the (meth)acryloyl group) may be linear, branched, or alicyclic. The number of carbon atoms of the alkyl group may be, for example, 1 to 30. The number of carbon atoms of the alkyl group may be 1 to 11, 1 to 8, 1 to 6, or 1 to 4, or may be 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0035] Examples of alkyl (meth) acrylates having a linear alkyl group include alkyl (meth) acrylates having a linear alkyl group with 1 to 11 carbon atoms, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, or undecyl (meth) acrylate, and alkyl (meth) acrylates having a linear alkyl group with 12 to 30 carbon atoms, such as dodecyl (meth) acrylate (lauryl (meth) acrylate), tetradecyl (meth) acrylate, hexadecyl (meth) acrylate (cetyl (meth) acrylate), octadecyl (meth) acrylate (stearyl (meth) acrylate), docosyl (meth) acrylate (behenyl (meth) acrylate), tetracosyl (meth) acrylate, hexacosyl (meth) acrylate, octacosyl (meth) acrylate.

[0036] Examples of alkyl (meth) acrylates having a branched alkyl group include alkyl (meth) acrylates having a branched alkyl group with 1 to 11 carbon atoms, such as s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, isopentyl (meth) acrylate, isoamyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, and alkyl (meth) acrylates having a branched alkyl group with 12 to 30 carbon atoms, such as isomyristyl (meth) acrylate, 2-propylheptyl (meth) acrylate, isoundecyl (meth) acrylate, isododecyl (meth) acrylate, isotridecyl (meth) acrylate, isopentadecyl (meth) acrylate, isohexadecyl (meth) acrylate, isoheptadecyl (meth) acrylate, isostearyl (meth) acrylate, decyltetradecanyl (meth) acrylate.

[0037] Examples of alkyl (meth)acrylates having an alicyclic alkyl group (cycloalkyl group) include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, terpene (meth)acrylate, dicyclopentanyl (meth)acrylate, and the like.

[0038] Examples of compounds having a (meth)acryloyl group and an aromatic hydrocarbon group include benzyl (meth)acrylate and the like.

[0039] Examples of compounds having a (meth)acryloyl group and a group containing a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, polybutylene glycol (meth)acrylate, methoxypolybutylene glycol (meth)acrylate, and the like.

[0040] Examples of compounds having a (meth)acryloyl group and a group containing a heterocycle include tetrahydrofurfuryl (meth)acrylate and the like.

[0041] Examples of compounds having a (meth)acryloyl group and an alkoxy group include 2-methoxyethyl acrylate and the like.

[0042] Examples of compounds having a (meth)acryloyl group and a phenoxy group include phenoxyethyl (meth)acrylate and the like.

[0043] Examples of compounds having a (meth)acryloyl group and a group containing a silane group include 3-acryloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

[0044] Examples of the compound having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylate and the like.

[0045] Examples of the compound having a (meth)acryloyl group and a halogen atom include (meth)acrylates having a fluorine atom such as trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl (meth)acrylate, perfluoroethyl methyl (meth)acrylate, perfluoropropyl methyl (meth)acrylate, perfluorobutyl methyl (meth)acrylate, perfluoropentyl methyl (meth)acrylate, perfluorohexyl methyl (meth)acrylate, perfluoroheptyl methyl (meth)acrylate, perfluorooctyl methyl (meth)acrylate, perfluorononyl methyl (meth)acrylate, perfluorodecyl methyl (meth)acrylate, perfluoroundecyl methyl (meth)acrylate, perfluorododecyl methyl (meth)acrylate, perfluorotridecyl methyl (meth)acrylate, perfluorotetradecyl methyl (meth)acrylate, 2-(trifluoromethyl)ethyl (meth)acrylate, 2-(perfluoroethyl)ethyl (meth)acrylate, 2-(perfluoropropyl)ethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluoropentyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluoroheptyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorononyl)ethyl (meth)acrylate, 2-(perfluorotridecyl)ethyl (meth)acrylate, 2-(perfluorotetradecyl)ethyl (meth)acrylate, etc.

[0046] Examples of the compound having a (meth)acryloyl group and a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate; and hydroxyalkyl cycloalkane (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.

[0047] Examples of the compound having a (meth)acryloyl group and a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, phthalic acid mono-hydroxyethyl acrylate (for example, "Aronix M5400" manufactured by Toagosei Co., Ltd.), and 2-acryloyloxyethyl succinate (for example, "NK Ester A-SA" manufactured by Shin-Nakamura Chemical Co., Ltd.).

[0048] Examples of the compound having a (meth)acryloyl group and an amino group include, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate and the like.

[0049] Examples of the compound having a (meth)acryloyl group and an epoxy group include glycidyl (meth)acrylate, glycidyl α-ethyl(meth)acrylate, glycidyl α-n-propyl(meth)acrylate, glycidyl α-n-butyl(meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 6,7-epoxyheptyl α-ethyl(meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxyhexyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-methylglycidyl α-ethyl(meth)acrylate, and the like.

[0050] The content of other polymerizable compounds may be, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, based on the total amount of the composition, and may be 99% by mass or less, 95% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, or 10% by mass or less.

[0051] The content of other polymerizable compounds may be, for example, 10 parts by mass or more, 20 parts by mass or more, 30 parts by mass or more, 40 parts by mass or more, 50 parts by mass or more, 60 parts by mass or more, 70 parts by mass or more, 80 parts by mass or more, or 90 parts by mass or more, based on 100 parts by mass in total of the content of polymerizable components, and may be 90 parts by mass or less, 80 parts by mass or less, 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.

[0052] The composition may further contain a polymerization initiator. The polymerization initiator may be, for example, a thermal polymerization initiator that generates radicals by heat, a photopolymerization initiator that generates radicals by light, or the like. The polymerization initiator is preferably a thermal polymerization initiator.

[0053] When the composition contains a thermal polymerization initiator, a cured product of the composition can be obtained by heating the composition. In this case, the composition may be a composition that is cured by heating preferably at 105°C or higher, more preferably at 110°C or higher, still more preferably at 115°C or higher, and for example, may also be a composition that is cured by heating at 200°C or lower, 190°C or lower, or 180°C or lower. The heating time when heating the composition may be appropriately selected according to the composition of the composition so that the composition is suitably cured.

[0054] Examples of the thermal polymerization initiator include azo compounds such as azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, and azodibenzoyl; organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxyhexahydroterephthalate, t-butyl peroxy-2-ethylhexanoate, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butyl peroxyisopropyl carbonate. The thermal polymerization initiator may be used alone or in combination of two or more thereof.

[0055] When the composition contains a photoinitiator, for example, by irradiating the composition with light (for example, light (ultraviolet light) containing at least a part of wavelengths of 200 to 400 nm), a cured product of the composition can be obtained. The conditions for light irradiation may be appropriately set according to the type of the photoinitiator.

[0056] Examples of the photoinitiator may include benzoin ether-based photoinitiators, acetophenone-based photoinitiators, α-ketol-based photoinitiators, aromatic sulfonyl chloride-based photoinitiators, photoactive oxime-based photoinitiators, benzoin-based photoinitiators, benzyl-based photoinitiators, benzophenone-based photoinitiators, ketal-based photoinitiators, thioxanthone-based photoinitiators, acylphosphine oxide-based photoinitiators, and the like.

[0057] Examples of benzoin ether-based photoinitiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one (e.g., "Irgacure 651" manufactured by BASF), anisole methyl ether, and the like. Examples of acetophenone-based photoinitiators include 1-hydroxycyclohexyl phenyl ketone (e.g., "Irgacure 184" manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (e.g., "Irgacure 2959" manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., "Irgacure 1173" manufactured by BASF), methoxyacetophenone, and the like.

[0058] Examples of α-ketol-based photoinitiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one, and the like. Examples of aromatic sulfonyl chloride-based photoinitiators include 2-naphthalenesulfonyl chloride, and the like. Examples of photoactive oxime-based photoinitiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime, and the like.

[0059] Examples of benzoin-based photoinitiators include benzoin. Examples of benzyl-based photoinitiators include benzyl. Examples of benzophenone-based photoinitiators include benzophenone, benzoyl benzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, etc. Examples of ketal-based photoinitiators include benzyldimethyl ketal. Examples of thioxanthone-based photoinitiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, etc.

[0060] As acylphosphine-based photoinitiators, there are bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,(6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethitoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tri(2-methylbenzoyl)phosphine oxide and the like can be mentioned.,

[0061] The above-mentioned photoinitiators may be used alone or in combination of two or more kinds.,

[0062] From the viewpoint of allowing the polymerization to proceed suitably, the content of the polymerization initiator is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, still more preferably 0.05 part by mass or more, with respect to 100 parts by mass in total of the content of the polymerizable components. From the viewpoint that the molecular weight of the polymer in the cured product of the composition is in a suitable range and suppressing decomposition products, the content of the polymerization initiator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, particularly preferably 1 part by mass or less, with respect to 100 parts by mass in total of the content of the polymerizable components.,

[0063] From the perspective of improving the thermal reliability of the cured product of the composition, the composition may further contain an antioxidant. The antioxidant may be, for example, a phenolic antioxidant, a benzophenone antioxidant, a benzoate antioxidant, a hindered amine antioxidant, a benzotriazole antioxidant, etc., and preferably a phenolic antioxidant.

[0064] The phenolic antioxidant has, for example, a hindered phenol structure (hindered phenol ring). The hindered phenol structure (hindered phenol ring) may be, for example, a structure in which a t-butyl group is bonded to one or both of the ortho positions relative to the hydroxyl group in the phenol ring. The phenolic antioxidant has one or more such hindered phenol rings, preferably two or more, more preferably three or more, and still more preferably four or more.

[0065] The content of the antioxidant may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, and may be 10% by mass or less, 9% by mass or less, 8% by mass or less, or 7% by mass or less based on the total amount of the composition.

[0066] The composition can further contain other additives as required. Examples of other additives include plasticizers (e.g., tackifiers), fillers (e.g., thermally conductive fillers), surface treatment agents (e.g., silane coupling agents), dispersants, curing accelerators, colorants, crystal nucleating agents, heat stabilizers, foaming agents, flame retardants, vibration damping agents, dehydrating agents, flame retardant aids (e.g., metal oxides), etc. The content of other additives may be 0.1% by mass or more and may be 30% by mass or less based on the total amount of the composition.

[0067] From the perspective of further improving the handleability, the composition is preferably liquid at 25°C. The composition may be solid at 25°C, and in that case, from the perspective of further improving the handleability, it is preferably made liquid by heating (e.g., at 50°C or higher).

[0068] [Composition set] According to one embodiment of the present invention, a multi-liquid composition set can be provided. The composition set according to one embodiment is a composition set including a first liquid containing an oxidizing agent and a second liquid containing a reducing agent. At least one of the first liquid and the second liquid contains the compound represented by the above formula (1). By mixing the first liquid and the second liquid, the oxidizing agent and the reducing agent react to generate free radicals, and the polymerization of polymerizable components such as the compound represented by the formula (1) proceeds. According to the composition set of the present embodiment, by mixing the first liquid and the second liquid, a cured product of the mixture of the first liquid and the second liquid can be obtained immediately. That is, according to the composition set, a cured product of the composition can be obtained at a high speed.

[0069] In the composition set, preferably, the first liquid contains an oxidizing agent and the compound represented by the formula (1), and the second liquid contains a reducing agent and the compound represented by the formula (1).

[0070] The content of the compound represented by the formula (1) based on the total amount of the liquids constituting the composition set (for example, in the case of a two-liquid composition set, the total amount of the first liquid and the second liquid) may be the same as the range of the content of the compound represented by the formula (1) based on the total amount of the above-described composition.

[0071] The oxidizing agent contained in the first liquid has a role as a polymerization initiator (radical polymerization initiator). The oxidizing agent may be, for example, an organic peroxide or an azo compound. The organic peroxide may be, for example, a hydroperoxide, a peroxydicarbonate, a peroxyester, a peroxyketal, a dialkyl peroxide, a diacyl peroxide, or the like. The azo compound may be AIBN (2,2'-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile), or the like. The oxidizing agent can be used alone or in combination of two or more.

[0072] Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0073] Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxy peroxydicarbonate, di(2-ethylhexylperoxy) dicarbonate, dimethoxybutyl peroxydicarbonate, di(3-methyl-3-methoxybutylperoxy) dicarbonate and the like.

[0074] Examples of the peroxyester include cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, t-hexyl peroxyneodecanoate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxyisobutyrate, 1,1-bis(t-butylperoxy) cyclohexane, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy) hexane, t-hexyl peroxybenzoate, t-butyl peroxyacetate and the like.

[0075] Examples of the peroxyketal include 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy) cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy) cyclododecane, 2,2-bis(t-butylperoxy) decane and the like.

[0076] Examples of the dialkyl peroxide include α,α'-bis(t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, t-butyl cumyl peroxide, and the like.

[0077] Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxytoluene, benzoyl peroxide, and the like.

[0078] From the viewpoint of storage stability, the oxidizing agent is preferably a peroxide, more preferably a hydroperoxide, and still more preferably cumene hydroperoxide.

[0079] The content of the oxidizing agent may be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, and may be 10% by mass or less, 5% by mass or less, or 3% by mass or less, based on the total amount of the liquids constituting the composition set.

[0080] The reducing agent contained in the second liquid may be, for example, a tertiary amine, a thiourea derivative, a transition metal salt, or the like. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N,N-dimethyl-p-toluidine, and the like. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylene thiourea, and the like. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, vanadyl acetylacetonate, and the like. The reducing agent can be used alone or in combination of two or more.

[0081] From the viewpoint of excellent curing speed, the reducing agent is preferably a thiourea derivative or a transition metal salt. The thiourea derivative may be, for example, ethylene thiourea. From the same viewpoint, the transition metal salt is preferably vanadyl acetylacetonate.

[0082] The content of the reducing agent may be 0.05% by mass or more, 0.1% by mass or more, or 0.3% by mass or more, and may be 5% by mass or less, 3% by mass or less, or 1% by mass or less, based on the total amount of the liquids constituting the composition set.

[0083] The composition set may further contain other polymerizable compounds and additives that can be used in the above-described composition. These components may be included in one or both of the first liquid and the second liquid, or may be included in a third liquid different from the first liquid and the second liquid. The content of these components based on the total amount of the liquids constituting the composition set may be the same as the range of the content of these components based on the total amount of the above-described composition.

[0084] The above-described composition or composition set has a low viscosity, and in its cured product, low elasticity, high elongation, and high strength can be realized. Therefore, it is suitable for applications such as thermally conductive materials (also called heat dissipation materials), adhesives, structural adhesives, battery binders, stress relievers, sealing agents, coating agents, paints, etc. Similarly, the cured product of the above-described composition or the cured product of the mixture of the composition set is suitable for each of the above applications because low elasticity, high elongation, and high strength can be realized.

Examples

[0085] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to the following examples.

[0086] In the examples, the following components were used. (A-1) A compound represented by the following formula (1-5) synthesized by the procedure shown below (weight average molecular weight: 8000, a mixture in which m in the formula (1-5) is an integer of approximately 180 ± 3, viscosity at 50°C: 10 Pa·s (solid at 25°C)) [Chemical formula] (A-2) A compound represented by formula (1-6) synthesized by the procedure shown below (weight-average molecular weight: 9400, a mixture in which m1 + m2 in formula (1-6) is approximately 160 ± 5 and n is an integer of approximately 38 ± 5, viscosity at 50 °C: 8 Pa·s (solid at 25 °C)) [Chemical formula] (A-3) A compound represented by formula (1-7) synthesized by the procedure shown below (weight-average molecular weight: 15000, a mixture in which m1 + m2 in formula (1-7) is approximately 252 ± 5 and n1 + n2 is an integer of approximately 63 ± 5 (however, m1 + n1 ≥ 100, m2 + n2 ≥ 100), viscosity at 25 °C: 50 Pa·s) [Chemical formula] In formula (1-7), -r- is a symbol representing random copolymerization. (A-4) A compound represented by formula (1-8) synthesized by the procedure shown below (weight-average molecular weight: 16000, a mixture in which m in formula (1-8) is approximately 246 ± 5 and n is an integer of approximately 105 ± 5, viscosity at 25 °C: 55 Pa·s) [Chemical formula] In formula (1-8), -r- is a symbol representing random copolymerization.

[0087] [Synthesis of the compound represented by formula (1-5)] A 500 mL flask composed of a stirrer, a thermometer, a nitrogen gas inlet tube, a discharge tube, and a heating jacket was used as a reactor. 120 g of polyethylene glycol #6000 and 300 g of toluene were added to the reactor, stirred at 45 °C and a stirring speed of 250 revolutions per minute, nitrogen was flowed at 100 mL / min, and stirred for 30 minutes. Then, the temperature was lowered to 25 °C. After the temperature drop was completed, 2.9 g of acryloyl chloride was added dropwise to the reactor and stirred for 30 minutes. Then, 3.8 g of triethylamine was added dropwise and stirred for 2 hours. Then, the temperature was raised to 45 °C and reacted for 2 hours. The reaction solution was filtered, and the filtrate was desolvated to obtain the compound represented by formula (1-5).

[0088] [Synthesis of each compound represented by formula (1-6) to (1-8)] In the method for synthesizing the compound represented by formula (1-5), the compound represented by formula (1-6) was obtained in the same manner except that polyethylene glycol #6000 was changed to polyoxyethylene polyoxypropylene glycol (141 g of "Newpole PE78" manufactured by Sanyo Chemical Industries, Ltd.). Also, in the method for synthesizing the compound represented by formula (1-5), the compound represented by formula (1-7) was obtained in the same manner except that polyethylene glycol #6000 was changed to a glycol having a polyoxyalkylene chain (225 g of "Newpole 75H-90000" manufactured by Sanyo Chemical Industries, Ltd.). Also, in the method for synthesizing the compound represented by formula (1-5), the compound represented by formula (1-8) was obtained in the same manner except that polyethylene glycol #6000 was changed to 240 g of polyoxyethylene polyoxypropylene glycol (molecular weight 16000).

[0089] In the examples and comparative examples, the following components were also used as needed in addition to the above. (a-1) A compound represented by the following formula (a-1) (weight average molecular weight: 1000, a mixture in which x in formula (a-1) is an integer of approximately 21 ± 3)

Chemical formula

Chemical formula

[0090] (B-1) 2-Ethylhexyl acrylate (manufactured by Nippon Shokubai Co., Ltd.) (B-2) 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (B-3) 2-Acryloyloxyethyl succinate (manufactured by Shin-Nakamura Chemical Co., Ltd. "NK Ester A-SA") (B-4) Isodecyl acrylate (manufactured by Hitachi Chemical Co., Ltd. "FA-111A") (C) Di-t-butyl peroxide (thermal polymerization initiator) (D) Rosin ester (plasticizer, manufactured by Arakawa Chemical Industries, Ltd. "Tackifier KE311")

[0091] [Preparation of Composition and Cured Product] Each component was mixed at the compounding ratios shown in Table 1 to obtain the compositions of the examples and comparative examples. Next, each composition was filled into a mold (made of SUS plate) of 10 cm × 10 cm × 0.2 mm, covered with a SUS plate lid, and then heated at 135 °C for 15 minutes to cure, thereby obtaining a cured product of the composition with a thickness of 0.2 mm.

[0092] [Measurement of Elongation at Break, Tensile Strength and Tensile Modulus] Using a tensile testing machine ("Autograph EZ-TEST EZ-S" manufactured by Shimadzu Corporation), the elongation at break, tensile modulus, and tensile strength at 25 °C of each cured product were measured. In the measurement, for a cured product with a shape of 0.2 mm (film thickness) × 5 mm (width) × 30 mm (length), based on JIS K7161, the measurement was carried out under the conditions of a chuck distance of 20 mm and a tensile speed of 5 mm / min.

[0093]

Table 1

[0094] As described above, since the components (A-1) to (A-4) used in Examples 1 to 9 had low viscosities at 25°C or 50°C, the compositions containing them were excellent in handleability. Further, the cured products of the said compositions showed high elongation at break.

Claims

1. A heat dissipation material composition containing a compound represented by the following formula (1), 【Chemical 1】 [In formula (1), R １１ and R １２ each independently represent a hydrogen atom or a methyl group, and R １３ represents a divalent group having a polyoxyalkylene chain.] wherein the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more.

2. The heat dissipation material composition according to Claim 1, wherein the polyoxyalkylene chain contains an oxyethylene group.

3. The heat dissipation material composition according to Claim 1, wherein the polyoxyalkylene chain contains an oxypropylene group.

4. The heat dissipation material composition according to Claim 1, wherein the polyoxyalkylene chain is a copolymer chain containing an oxyethylene group and an oxypropylene group.

5. The heat dissipation material composition according to Claim 4, wherein the copolymer chain is a random copolymer chain.

6. The heat dissipation material composition according to any one of Claims 1 to 5, wherein the weight average molecular weight of the compound represented by the formula (1) is 5000 or more.

7. The heat dissipation material composition according to any one of Claims 1 to 6, wherein the viscosity of the compound represented by the formula (1) at 25°C is 200 Pa·s or less.

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