Composition containing a compound having a polyoxyalkylene chain

Abstract

A compound containing the compound represented by the following formula (1), [Chemical 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.] A composition having 100 or more oxyalkylene groups in a polyoxyalkylene chain.

Description

Technology Field

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

[0002] For electronic components that generate heat during use, a thermally conductive material called a thermal interface material (TIM) (sometimes referred to as a heat dissipation material) is used to efficiently dissipate heat. TIMs include, for example, a polymer and a thermally conductive filler.

[0003] Polymers as described above are selected to be suitable depending on the application (target) of the TIM. Specifically, for example, there are cases where a composition containing a polymer is required to have low viscosity and excellent handling properties, and the cured product of said composition is required to have low elasticity. In this regard, for example, Patent Document 1 discloses a curable silicone composition that forms a cured product with good handling properties and a low modulus of elasticity. Prior art literature

[0004] Patent Document 1: Japanese Published Patent Application No. 2008-081676 The problem to be solved

[0005] According to the inventors' review, in cured products of compositions with improved handling properties using low-viscosity polymers, there are cases where it is required to have a high elongation at break. However, achieving these simultaneously is not necessarily easy.

[0006] Accordingly, the present invention aims to improve the breakage elongation rate of the cured product of the composition while improving the handling properties of the composition. means of solving the problem

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

[0008] [1]

[0009] A compound containing the compound represented by the following formula (1),

[0010] [Chemical Formula 1]

[0011]

[0012] [In Equation (1), R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, and R 13 [It represents a divalent group having a polyoxyalkylene chain.]

[0013] A composition having 100 or more oxyalkylene groups in a polyoxyalkylene chain.

[0014] [2]

[0015] A composition described in [1] in which the polyoxyalkylene chain contains an oxyethylene group.

[0016] [3]

[0017] A composition described in [1] in which the polyoxyalkylene chain comprises an oxypropylene group.

[0018] [4]

[0019] A composition described in [1] in which the polyoxyalkylene chain is a copolymer chain comprising oxyethylene and oxypropylene groups.

[0020] [5]

[0021] A composition described in [4] in which the copolymer chain is a random copolymer chain.

[0022] [6]

[0023] A composition described in any one of [1] to [5] having a weight average molecular weight of 5000 or more of the compound represented by formula (1).

[0024] [7]

[0025] A composition described in 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. Effects of the invention

[0026] According to the present invention, the fracture elongation rate of the cured product of the composition can be improved while improving the handling properties of the composition. Specific details for implementing the invention

[0027] Embodiments of the present invention will be described in detail below. Furthermore, the present invention is not limited to the following embodiments.

[0028] In this specification, "(meth)acryloyl" means "acryloyl" and the corresponding "methacryloyl," and the same applies to similar expressions such as "(meth)acrylate" and "(meth)acryl."

[0029] In this specification, the weight average molecular weight (Mw) refers to a value determined using polystyrene as a standard material, measured under the following conditions using gel permeation chromatography (GPC).

[0030] · Measuring instrument: HLC-8320GPC (Product name, manufactured by Doso Co., Ltd.)

[0031] · Analysis Column: TSKgel SuperMultipore HZ-H (3-piece connection) (Product Name, Manufactured by Doso Co., Ltd.)

[0032] · Guard Column: TSKguardcolumn SuperMP(HZ)-H (Product Name, Manufactured by Doso Co., Ltd.)

[0033] · Eluent: THF

[0034] · Measured temperature: 25℃

[0035] One embodiment of the present invention is a composition containing a compound represented by the following formula (1).

[0036] [Chemical Formula 2]

[0037]

[0038] In Equation (1), R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, and R 13 It represents a divalent group having a polyoxyalkylene chain.

[0039] In one embodiment, R 11 and R 12 One side may be a hydrogen atom and the other side may be a methyl group, and in another embodiment, R 11 and R 12 Both sides may be hydrogen atoms, and in another embodiment, R 11 and R 12 Both sides of the methyl group may be methylated.

[0040] The number of oxyalkylene groups in the above polyoxyalkylene chain is 100 or more. The composition of the present embodiment has a structure represented by Formula (1), and by containing a compound having 100 or more oxyalkylene groups in the polyoxyalkylene chain, it is possible to form a cured product with low viscosity, excellent handling properties, and excellent elongation at break. In addition, in one embodiment, the cured product of this composition may have low elasticity and high strength. In this regard, 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.

[0041] In one embodiment, the polyoxyalkylene chain includes an oxyethylene group (in other words, a structural unit represented by the following formula (2)). This allows for a higher strength of the cured product while further suppressing the increase in viscosity of the composition.

[0042] [Chemical Formula 3]

[0043]

[0044] In this case, R 13 The compound represented by Formula (1), which has a polyoxyethylene chain and contributes to a divalent structure, is preferably the compound represented by Formula (1-2) (polyethylene glycol di(meth)acrylate).

[0045] [Chemical Formula 4]

[0046]

[0047] In Equation (1-2), R 11 and R 12 is R in Equation (1) 11 and R 12 Each has the same meaning as, and m is an integer greater than or equal to 100. m can take lower and upper limits equal to the number of oxyalkylene groups described above.

[0048] In another embodiment, the polyoxyalkylene chain includes an oxypropylene group (in other words, a structural unit represented by the following formula (3)). This makes it easier to handle the composition.

[0049] [Chemical Formula 5]

[0050]

[0051] In this case, R 13 The compound represented by Formula (1) is a divalent compound having a polyoxypropylene chain, and is preferably a compound represented by Formula (1-3) (polypropylene glycol di(meth)acrylate).

[0052] [Chemical Formula 6]

[0053]

[0054] In Equation (1-3), R 11 and R 12 is R in Equation (1) 11 and R 12 Each has the same meaning, and n is an integer greater than or equal to 100. m can take lower and upper limits equal to the number of oxyalkylene groups described above.

[0055] In another embodiment, the polyoxyalkylene chain is preferably a copolymer chain comprising oxyethylene groups and oxypropylene groups, in order to make it easier to achieve the handling properties of the composition and the low elasticity, high elongation, and high strength of the cured product. 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, in order to make the handling of the composition easier.

[0056] In each of the embodiments described above, the polyoxyalkylene chain may have, in addition to the oxyethylene group and oxypropylene group, 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.

[0057] R 13 In addition to the polyoxyalkylene chain described above, it may also be a divalent contribution having other organic groups. The other organic groups may be chain-like contributions other than the polyoxyalkylene chain, and may be, for example, a methylene chain (a chain with -CH2- as a structural unit), a polyester chain (a chain containing -COO- as a structural unit), a polyuretic chain (a chain containing -OCON- as a structural unit), etc.

[0058] For example, the compound represented by formula (1) may be the compound represented by the following formula (1-4).

[0059] [Chemical Formula 7]

[0060]

[0061] In Equation (1-4), R 11 and R 12 is R in Equation (1) 11 and R 12 and have the same meaning respectively, and R 14 and R 15 Each is independently an alkylene group having 2 to 5 carbon atoms, k1 and k3 are each independently integers greater than or equal to 100, and k2 is an integer greater than or equal to 2.

[0062] k1 and k3 may each independently take a lower and upper limit equal to the number of oxyalkylene groups described above. k2 may be, for example, an integer of 16 or less.

[0063] R that exists in multiple places 14 and R 15 Each may be identical to or different from one another. Multiple Rs exist. 14 and R 15 Each includes, preferably, an ethylene group and a propylene group. That is, (R 14 O) k1 Polyoxyalkylene chains appearing as, and (R 15 O) k3 The polyoxyalkylene chains shown are, each preferably, copolymer chains containing oxyethylene groups and oxypropylene groups.

[0064] 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 perspective of making it easier to adjust the viscosity of the composition. 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 perspective of making it easier to adjust the viscosity of the composition.

[0065] The compound represented by Formula (1) may be in a liquid state 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, even more preferably 300 Pa·s or less, and particularly preferably 200 Pa·s or less, from the viewpoint of further improving the handling properties 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.

[0066] The compound represented by Formula (1) may be in a solid state at 25°C. In this case, from the view of further improving the handling properties of the composition, the compound represented by Formula (1) is preferably in a liquid state 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, even more preferably 30 Pa·s or less, and particularly preferably 20 Pa·s or less, from the view of further improving the handling properties 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.

[0067] Viscosity refers to a value measured in accordance with JIS Z 8803, specifically, a value measured by an E-type viscometer (e.g., PE-80L manufactured by Toki Sangyo Co., Ltd.). Additionally, the viscometer can be calibrated in accordance with JIS Z 8809-JS14000. The viscosity of the compound represented by Equation (1) can be adjusted by adjusting the weight-average molecular weight of the compound.

[0068] The content of the compound represented by formula (1) may be, based on the total amount of the composition, for example, 1 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more, or 99 mass% or less, 95 mass% or less, 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less.

[0069] The composition may contain only the compound represented by Formula (1) as the polymerizable compound. The composition may further contain other polymerizable compounds other than the compound represented by Formula (1) (details will be described later). In this case, the content of the compound represented by 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, with respect to 100 parts by mass of the total of the compound represented by formula (1) and other polymerizable compounds (hereinafter referred to as "total content of polymerizable components"), or 90 parts by mass or more, or 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.

[0070] The composition may further contain other polymerizable compounds capable of copolymerizing with the compound represented by the above-described formula (1) for purposes such as adjusting the physical properties of the composition.

[0071] Other polymerizable compounds may be, for example, compounds having one (meth)acryloyl group. Such compounds may be, for example, alkyl (meth)acrylates. Other polymerizable compounds may be compounds having, in addition to one (meth)acryloyl group, aromatic hydrocarbon groups, groups containing polyoxyalkylene chains, groups containing heterocyclic groups, alkoxy groups, phenoxy groups, groups containing silane groups, groups containing siloxane bonds, halogen atoms, hydroxyl groups, carboxyl groups, amino groups, or epoxy groups. In particular, the viscosity of the composition can be adjusted by the composition containing alkyl (meth)acrylates. Furthermore, the adhesion of the composition and the cured product to the substrate can be further improved by the composition containing a compound having, in addition to the (meth)acryloyl group, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group.

[0072] The alkyl group (alkyl group portion other than the (meth)acryloyl group) in the alkyl (meth)acrylate may be straight-chain, branched, or alicyclic. The number of carbon atoms in the alkyl group may be, for example, 1 to 30. The number of carbon atoms in the alkyl group may be 1 to 11, 1 to 8, 1 to 6, or 1 to 4, or 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0073] As alkyl (meth)acrylates having a straight-chain alkyl group, alkyl (meth)acrylates having a straight-chain alkyl group having 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; dodecyl (meth)acrylate (lauryl (meth)acrylate); tetradecyl (meth)acrylate; hexadecyl (meth)acrylate (cetyl (meth)acrylate); octadecyl (meth)acrylate (stearyl (meth)acrylate) Examples include alkyl (meth)acrylates having straight-chain alkyl groups having 12 to 30 carbon atoms, such as docosil (meth)acrylate (behenyl (meth)acrylate), tetracosil (meth)acrylate, hexacosil (meth)acrylate, and octacosil (meth)acrylate.

[0074] As alkyl (meth)acrylates having a branched alkyl group, alkyl (meth)acrylates having a branched alkyl group having 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, and isodecyl (meth)acrylate; isomyristyl (meth)acrylate; 2-propylheptyl (meth)acrylate; isoundecyl (meth)acrylate; isododecyl (meth)acrylate; isotridecyl (meth)acrylate; and isopentadecyl (meth)acrylate. Examples include alkyl (meth)acrylates having a branched alkyl group having 12 to 30 carbon atoms, such as isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, isostearyl (meth)acrylate, and decyltetradecaneyl (meth)acrylate.

[0075] Examples of alkyl (meth)acrylates having a cycloalkyl group (cycloalkyl group) include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, terpene (meth)acrylate, dicyclopentanyl (meth)acrylate, etc.

[0076] Examples of compounds having (meth)acryloyl groups and aromatic hydrocarbon groups include benzyl (meth)acrylate.

[0077] Examples of compounds having a group including a (meth)acryloyl group and 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, etc.

[0078] Examples of compounds having a (meth)acryloyl group and a heterocyclic group include tetrahydrofurfuryl (meth)acrylate.

[0079] Examples of compounds having (meth)acryloyl groups and alkoxy groups include 2-methoxyethylacrylate.

[0080] Examples of compounds having (meth)acryloyl groups and phenoxy groups include phenoxyethyl (meth)acrylate.

[0081] Examples of compounds having a group including a (meth)acryloyl group and a silane group include 3-acryloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltriethoxysilane, and 10-acryloyloxydecyltriethoxysilane.

[0082] Examples of compounds having a (meth)acryloyl group and a group including a siloxane bond include silicon (meth)acrylate.

[0083] Compounds having a (meth)acryloyl group and a halogen atom include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl (meth)acrylate, perfluoroethylmethyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, perfluorobutylmethyl (meth)acrylate, perfluoropentylmethyl (meth)acrylate, perfluorohexylmethyl (meth)acrylate, perfluoroheptylmethyl (meth)acrylate, perfluorooctylmethyl (meth)acrylate, perfluorononylmethyl (meth)acrylate, perfluorodecylmethyl (meth)acrylate, perfluoroundecylmethyl (meth)acrylate, perfluorododecylmethyl (meth)acrylate, and perfluorotridecylmethyl (meth)acrylate. Examples of (meth)acrylates having fluorine atoms include perfluorotetradecylmethyl(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, and 2-(perfluorotetradecyl)ethyl(meth)acrylate.

[0084] Examples of compounds having (meth)acryloyl and hydroxyl groups 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, and 12-hydroxylauryl (meth)acrylate; and hydroxyalkyl cycloalkanes (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.

[0085] Examples of compounds having (meth)acryloyl and carboxyl groups include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, phthalate monohydroxyethyl acrylate (e.g., "Aronix M5400" manufactured by Doa Kosei Co., Ltd.), and 2-acryloyloxyethylsuccinate (e.g., "NK Ester A-SA" manufactured by Shinnakamura Kagaku Co., Ltd.).

[0086] Examples of compounds having (meth)acryloyl groups and amino groups include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, etc.

[0087] Compounds having (meth)acryloyl groups and epoxy groups include, for example, (meth)acrylate glycidyl, α-ethyl(meth)acrylate glycidyl, α-n-propyl(meth)acrylate glycidyl, α-n-butyl(meth)acrylate glycidyl, (meth)acrylate-3,4-epoxybutyl, (meth)acrylate-4,5-epoxypentyl, (meth)acrylate-6,7-epoxyheptyl, α-ethyl(meth)acrylate-6,7-epoxyheptyl, (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, Examples include α-ethyl(meth)acrylic acid-β-methylglycidyl.

[0088] The content of other polymerizable compounds, based on the total amount of the composition, may be, for example, 1 mass% or more, 5 mass% or more, 10 mass% or more, 20 mass% or more, 30 mass% or more, 40 mass% or more, 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more, or 99 mass% or less, 95 mass% or less, 90 mass% or less, 80 mass% or less, 70 mass% or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less.

[0089] 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, with respect to 100 parts by mass of the total content of polymerizable components.

[0090] 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, etc. The polymerization initiator is preferably a thermal polymerization initiator.

[0091] When the composition contains a thermal polymerization initiator, a cured product of the composition can be obtained by adding heat to the composition. In this case, the composition may be a composition that is cured by heating at a temperature preferably 105°C or higher, more preferably 110°C or higher, and even more preferably 115°C or higher, or may be a composition that is cured by heating at, for example, 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.

[0092] Examples of thermal polymerization initiators include azo compounds such as azobis-isobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobis-cyclohexanone-1-carbonitrile, and azodibenzoyl; organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-t-butylperoxide, di-t-hexyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-t-butylperoxy-3,3,5-trimethylcyclohexane, and t-butylperoxyisopropylcarbonate. The thermal polymerization initiators may be used as a single type or in combination of two or more of these.

[0093] When the composition contains a photopolymerization initiator, for example, a cured product of the composition can be obtained by irradiating the composition with light (e.g., light including at least some wavelengths of 200 to 400 nm (ultraviolet light)). The conditions for light irradiation may be appropriately set according to the type of photopolymerization initiator.

[0094] The photopolymerization initiator may be, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a benzophenone-based photopolymerization initiator, a ketal-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, etc.

[0095] Examples of benzoin ether-based photopolymerization initiators 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., BASF’s "Irgacure 651"), anisole methyl ether, etc. Examples of acetophenone-based photopolymerization initiators include 1-hydroxycyclohexylphenylketone (e.g., BASF's "Irgacure 184"), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (e.g., BASF's "Irgacure 2959"), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., BASF's "Irgacure 1173"), methoxyacetophenone, etc.

[0096] Examples of α-ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one. Examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride. Examples of photoactive oxime photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

[0097] Examples of benzoin-based photopolymerization initiators include benzoin. Examples of benzyl-based photopolymerization initiators include benzyl. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexylphenylketone, etc. Examples of ketal-based photopolymerization initiators include benzyldimethylketal. Examples of thioxantone-based photopolymerization initiators include thioxantone, 2-chlorothioxantone, 2-methylthioxantone, 2,4-dimethylthioxantone, isopropylthioxantone, 2,4-dichlorothioxantone, 2,4-diethylthioxantone, isopropylthioxantone, 2,4-diisopropylthioxantone, dodecylthioxantone, etc.

[0098] As acylphosphine-based photopolymerization initiators, 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-methylpropane-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropane-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-methylpropane-1-yl)phosphine oxide, Bis(2-methoxybenzoyl)(1-methylpropane-1-yl)phosphine oxide, Bis(2,6-diethoxybenzoyl)(2-methylpropane-1-yl)phosphine oxide, Bis(2,6-diethoxybenzoyl)(1-methylpropane-1-yl)phosphine oxide, Bis(2,6-dibutoxybenzoyl)(2-methylpropane-1-yl)phosphine oxide, Bis(2,4-dimethoxybenzoyl)(2-methylpropane-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,Examples include 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-dimethoxybenzoyl-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, etc.

[0099] The above-described photopolymerization initiator may be used as a single type or in combination of two or more types.

[0100] The content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.05 parts by mass or more, with respect to suitably carrying out polymerization, with respect to suppressing decomposition products and ensuring that the molecular weight of the polymer in the cured product of the composition is within a suitable range, with respect to the total content of the polymerization initiator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, with respect to the total content of the polymerization initiator is 100 parts by mass or less, with respect to the total content of the polymerization initiator.

[0101] The composition may further contain an antioxidant in order to improve the thermal reliability of the cured product of the composition. The antioxidant may be, for example, a phenolic antioxidant, a benzophenone antioxidant, a benzoate antioxidant, a hindered antioxidant. It may be an amine-based antioxidant, a benzotriazole-based antioxidant, etc., and preferably a phenol-based antioxidant.

[0102] Phenolic antioxidants have, 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 attached to one or both of the ortho positions with respect to the hydroxyl group in the phenol ring. Phenolic antioxidants have one or more such hindered phenol rings, preferably two or more, more preferably three or more, and even more preferably four or more.

[0103] The content of the antioxidant may be 0.1 mass% or more, 0.2 mass% or more, or 0.3 mass% or more based on the total amount of the composition, and may be 10 mass% or less, 9 mass% or less, 8 mass% or less, or 7 mass% or less.

[0104] The composition may additionally contain other additives as needed. 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, coloring agents, crystallization nucleating agents, heat stabilizers, foaming agents, flame retardants, vibration dampeners, dehydrating agents, flame retardant aids (e.g., metal oxides), etc. The content of other additives may be 0.1 mass% or more and 30 mass% or less based on the total amount of the composition.

[0105] The composition is preferably in a liquid state at 25°C to further improve handling. The composition may be in a solid state at 25°C, in which case it is preferably to become a liquid state upon heating (e.g. at 50°C or higher) to further improve handling.

[0106] [Composition Set]

[0107] According to one embodiment of the present invention, a set of compositions of multiple liquid types can be provided. A set of compositions according to one embodiment is a set of compositions comprising 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 a compound represented by the formula (1) described above. By mixing the first liquid and the second liquid, the oxidizing agent and the reducing agent react to generate free radicals, and polymerization of a polymerizable component, such as the compound represented by the formula (1), proceeds. According to the set of compositions according to this embodiment, a cured product of the mixture of the first liquid and the second liquid is obtained immediately by mixing the first liquid and the second liquid. That is, according to the set of compositions, a cured product of the composition is obtained at a rapid rate.

[0108] In the composition set, preferably, the first liquid contains an oxidizing agent and a compound represented by formula (1), and the second liquid contains a reducing agent and a compound represented by formula (1).

[0109] The content of the compound represented by Formula (1), based on the total amount of liquid constituting the composition set (for example, if it is a two-component 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 Formula (1), based on the total amount of the composition described above.

[0110] The oxidizing agent included in the first liquid serves 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, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, diacyl peroxide, etc. The azo compound may be AIBN (2,2'-azobis-isobutyronitrile), V-65 (azobis-dimethylvaleronitrile), etc. The oxidizing agent may be used as a single type or in combination of two or more types.

[0111] Examples of hydroperoxides include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0112] Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutylperoxydicarbonate, di(3-methyl-3-methoxybutylperoxy)dicarbonate, etc.

[0113] As peroxyesters, cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexane-oilperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, Examples include t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-hexylperoxybenzoate, t-butylperoxyacetate, etc.

[0114] Examples of peroxyketals 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.

[0115] Examples of dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, etc.

[0116] Examples of diasyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexane euyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxytoluene, benzoyl peroxide, etc.

[0117] The oxidizing agent is, in terms of storage stability, preferably a peroxide, more preferably a hydroperoxide, and even more preferably a cumene hydroperoxide.

[0118] The content of the oxidizing agent may be 0.1 mass% or more, 0.5 mass% or more, or 1 mass% or more based on the total amount of liquid constituting the composition set, or 10 mass% or less, 5 mass% or less, or 3 mass% or less.

[0119] The reducing agent included in the second liquid may be, for example, a tertiary amine, a thiourea derivative, a transition metal salt, etc. Examples of tertiary amines include triethylamine, tripropylamine, tributylamine, N,N-dimethylparatoluidine, etc. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea, etc. Examples of transition metal salts include cobalt naphthenate, copper naphthenate, vanadylacetylacetonate, etc. The reducing agent may be used as a single type or in combination of two or more types.

[0120] The reducing agent is preferably a thiourea derivative or a transition metal salt, in terms of excellent curing speed. The thiourea derivative may be, for example, ethylenethiourea. In the same regard, the transition metal salt is preferably vanadylacetylacetonate.

[0121] The content of the reducing agent may be 0.05 mass% or more, 0.1 mass% or more, or 0.3 mass% or more, based on the total amount of liquid constituting the composition set, or 5 mass% or less, 3 mass% or less, or 1 mass% or less.

[0122] The composition set may further contain other polymerizable compounds and additives that can be used in the composition described above. These components may be included in either or both of the first and second liquids, or may be included in a third liquid that is different from the first and second liquids. The content of these components based on the total amount of the liquid constituting the composition set may be the same as the range of the content of these components based on the total amount of the composition described above.

[0123] The above-described composition or set of compositions is suitable for applications such as thermally conductive materials (also called heat dissipation materials), adhesives, structural adhesives, battery binders, stress relievers, sealants, coatings, and paints, as the cured product can achieve low elasticity, high elongation, and high strength while having low viscosity. Likewise, the cured product of the above-described composition or the cured product of the mixture of the set of compositions is suitable for each of the above applications because it can achieve low elasticity, high elongation, and high strength.

[0124] Examples

[0125] The present invention will be explained more specifically below by way of examples, but the present invention is not limited to the following examples.

[0126] In the examples, each of the following components was used.

[0127] (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 formula (1-5) is an integer of approximately 180±3, viscosity at 50°C: 10 Pa·s (solid at 25°C))

[0128] [Chemical Formula 8]

[0129]

[0130] (A-2) Compound represented by Formula (1-6) synthesized by the procedure shown below (weight average molecular weight: 9400, 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))

[0131] [Chemical Formula 9]

[0132]

[0133] (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 approximately 63±5 (where m1+n1≥100 and m2+n2≥100), viscosity at 25°C: 50 Pa·s)

[0134] [Chemical Formula 10]

[0135]

[0136] In Equation (1-7), -r- is a symbol indicating random copolymerization.

[0137] (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 an integer of 246±5 and n is approximately an integer of 105±5, viscosity at 25°C: 55 Pa·s)

[0138] [Chemical Formula 11]

[0139]

[0140] In Equation (1-8), -r- is a symbol indicating random copolymerization.

[0141] [Synthesis of the compound represented by Equation (1-5)]

[0142] A 500 mL flask comprising a stirrer, thermometer, nitrogen gas inlet tube, exhaust tube, and heating jacket was used as a reactor. 120 g of polyethylene glycol #6000 and 300 g of toluene were added to the reactor. The mixture was stirred at 45°C with a stirring speed of 250 revolutions / min, and nitrogen was flowed at 100 mL / min for 30 minutes. Afterward, the temperature was lowered to 25°C. Once the cooling was complete, 2.9 g of acryloyl chloride was added dropwise to the reactor and stirred for 30 minutes. Subsequently, 3.8 g of triethylamine was added dropwise and stirred for 2 hours. Afterward, the temperature was raised to 45°C and the reaction was carried out for 2 hours. The reaction mixture was filtered, and the filtrate was precipitated to obtain the compound represented by Formula (1-5).

[0143] [Synthesis of each compound represented by Equations (1-6) to (1-8)]

[0144] In the method of synthesizing the compound represented by Formula (1-5), the compound represented by Formula (1-6) was obtained by the same method, except that polyethylene glycol #6000 was changed to polyoxyethylene polyoxypropylene glycol (141 g of "Nyupol PE78" manufactured by Sanyo Kasei Co., Ltd.). In addition, in the method of synthesizing the compound represented by Formula (1-5), the compound represented by Formula (1-7) was obtained by the same method, except that polyethylene glycol #6000 was changed to a glycol having polyoxyalkylene chains (225 g of "Nyupol 75H-90000" manufactured by Sanyo Kasei Co., Ltd.). In addition, in the method of synthesizing the compound represented by Formula (1-5), the compound represented by Formula (1-8) was obtained by the same method, except that polyethylene glycol #6000 was changed to 240 g of polyoxyethylene polyoxypropylene glycol (molecular weight 16000).

[0145] In the examples and comparative examples, in addition to the above, each of the following components was also used as needed.

[0146] (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)

[0147] [Chemical Formula 12]

[0148]

[0149] (a-2) Compounds represented by the following formula (a-2) (weight-average molecular weight: 700, mixtures in which y in formula (a-2) is an integer of approximately 11±3)

[0150] [Chemical Formula 13]

[0151]

[0152] (a-3) A compound represented by the above formula (a-2) (weight average molecular weight: 4000, a mixture in which y in formula (a-2) is an integer of approximately 58±3)

[0153] (B-1) 2-ethylhexyl acrylate (Nippon Shokubai Co., Ltd.)

[0154] (B-2) 4-Hydroxybutylacrylate (Manufactured by Osaka Yuki Kagaku High School Co., Ltd.)

[0155] (B-3) 2-Acryloyloxyethylsuccinate (Shin-Nakamura Kogyo Co., Ltd. "NK Ester A-SA")

[0156] (B-4) Isodecyl acrylate (Hitachi Kasei Corporation "FA-111A")

[0157] (C) Di-t-butyl peroxide (thermal polymerization initiator)

[0158] (D) Rosin ester (plasticizer, "Tackyfire KE311" manufactured by Arakawa Kagaku Kogyo Co., Ltd.)

[0159] [Preparation of Composition and Cured Material]

[0160] Each component was mixed according to the mixing 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) measuring 10 cm × 10 cm × 0.2 mm, and after covering the top with a SUS plate, the composition was heated and cured at 135°C for 15 minutes to obtain a cured product of the composition with a thickness of 0.2 mm.

[0161] [Measurement of fracture elongation, fracture strength, and tensile modulus]

[0162] Using a tensile testing machine ("Autograph EZ-TEST EZ-S" manufactured by Shimadzu Seisakusho Inc.), the elongation at break, tensile modulus, and strength at break of each cured product at 25°C were measured. For the measurement, a cured product with a shape of 0.2 mm (film thickness) × 5 mm (width) × 30 mm (length) was measured based on JIS K7161 under conditions of a zipper distance of 20 mm and a tensile speed of 5 mm / min.

[0163] [Table 1]

[0164]

[0165] As described above, since the components (A-1) to (A-4) used in Examples 1 to 9 have low viscosity at 25°C or 50°C, the compositions containing them had excellent handling properties. In addition, the cured products of the compositions exhibited a high elongation at break.

Claims

Claim 1 A compound represented by the following formula (1), and another polymerizable compound having one (meth)acryloyl group that is copolymerizable with the compound represented by the following formula (1), containing at least 1 mass% based on the total amount of the composition, [Chemical Formula 1] [In Equation (1), R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, and R 13 [Represents a divalent group having a polyoxyalkylene chain.] A composition in which the polyoxyalkylene chain is a copolymer chain comprising an oxyethylene group and an oxypropylene group, and the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more. Claim 2 delete Claim 3 delete Claim 4 delete Claim 5 A composition according to claim 1, wherein the copolymer chain is a random copolymer chain. Claim 6 A composition according to claim 1, wherein the weight average molecular weight of the compound represented by formula (1) is 5000 or more. Claim 7 A composition according to any one of claims 1, 5 and 6, wherein the viscosity of the compound represented by formula (1) at 25°C is 200 Pa·s or less.

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