A set of compositions containing compounds having polyoxyalkylene chains.

Abstract

To improve the handling properties of the composition set while also improving the elongation at break of the cured product of the composition set. [Solution] A composition set comprising a first liquid containing an oxidizing agent and a second liquid containing a reducing agent, wherein at least one of the first liquid and the second liquid contains a compound represented by the following formula (1), TIFF2026076327000012.tif33149 [In formula (1), R 11 and R 12 Each of these independently represents a hydrogen atom or a methyl group, R 13 This represents a divalent group having a polyoxyalkylene chain. A set of compositions in which the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more.

Description

[Technical Field]

[0001] The present invention relates to a set of compositions containing compounds having polyoxyalkylene chains. [Background technology]

[0002] In electronic components and other devices that generate heat during use, thermal interface materials (TIMs), which are thermally conductive materials (sometimes called heat dissipation materials), are used to efficiently dissipate heat. TIMs, for example, contain polymers and thermally conductive fillers.

[0003] The polymers described above are selected according to their suitability for the application (target) of the TIM. Specifically, for example, compositions containing polymers may require low viscosity and excellent handling properties, while the cured product of the composition set may require low elasticity. In response to this, for example, Patent Document 1 discloses a curable silicone composition that has good handling properties and forms a cured product with a low modulus of elasticity. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-081676 [Overview of the project] [Problems that the invention aims to solve]

[0005] According to our research, in multi-component (e.g., two-component) composition sets, when handling is improved using low-viscosity polymers, it is sometimes required to increase the elongation at break of the cured product of the composition set. However, achieving both simultaneously is not always easy.

[0006] Therefore, the present invention aims to improve the handling of the composition set while improving the elongation at break of the cured product of the composition set. [Means for Solving the Problems]

[0007] As a result of intensive studies, the present inventors have found that a composition set 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 some aspects.

[0008] [1] A composition set comprising a first liquid containing an oxidizing agent and a second liquid containing a reducing agent, wherein at least one of the first liquid and the second liquid contains 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 set in which the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more. [2] The composition set according to [1], wherein the polyoxyalkylene chain contains an oxyethylene group. [3] The composition set according to [1], wherein the polyoxyalkylene chain contains an oxypropylene group. [4] The composition set according to [1], wherein the polyoxyalkylene chain is a copolymer chain containing an oxyethylene group and an oxypropylene group. [5] The composition set according to [4], wherein the copolymer chain is a random copolymer chain. [6] The composition set 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 set according to any one of [1] to [?], wherein the viscosity of the compound represented by formula (1) at 25 ° C is 200 Pa·s or less. [Advantages of the Invention] It should be noted that there seems to be a typo in the original text where [1] to [?] is mentioned in item [7]. It should probably be [1] to [6]. The translation is done according to the provided rules while keeping the possible error in the original text as it is.

[0009] According to the present invention, while improving the handleability of the composition set, the elongation at break of the cured product of the composition set can be improved.

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 its 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 · Measuring temperature: 25°C

[0013] The composition set according to one embodiment includes a first liquid containing an oxidizing agent and a second liquid containing a reducing agent. 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 following 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 (hereinafter, this cured product is also referred to as “cured product of the composition set”) can be obtained. The first liquid and the second liquid may be liquid at, for example, 25°C.

[0014] The oxidizing agent contained in the first solution acts as a polymerization initiator (radical polymerization initiator). The oxidizing agent may be, for example, an organic peroxide or an azo compound. Examples of organic peroxides include hydroperoxides, peroxydicarbonates, peroxyesters, peroxyketals, dialkylperoxides, diacylperoxides, etc. Examples of azo compounds include AIBN (2,2'-azobisisobutyronitrile) and V-65 (azobisdimethylvaleronitrile). The oxidizing agent can be used alone or in combination of two or more types.

[0015] Examples of hydroperoxides include diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and cumene hydroperoxide.

[0016] Examples of peroxydicarbonates include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxymethoxyperoxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutylperoxy)dicarbonate.

[0017] Examples of peroxyesters 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, and 1-cyclohexyl-1-methylethyl peroxy Examples include t-2-ethylhexanate, t-hexylperoxy-2-ethylhexanate, t-butylperoxy-2-ethylhexanate, t-butylperoxyisobutyrate, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxy-3,5,5-trimethylhexanate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, t-hexylperoxybenzoate, and t-butylperoxyacetate.

[0018] 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, and 2,2-bis(t-butylperoxy)decane.

[0019] Examples of dialkyl peroxides include α,α'-bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, and t-butylcumyl peroxide.

[0020] Examples of diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic peroxide, benzoyl peroxytoluene, and benzoyl peroxide.

[0021] The oxidizing agent is preferably a peroxide, more preferably a hydroperoxide, even more preferably 1,1,3,3-tetramethylbutyl hydroperoxide or cumene hydroperoxide, and particularly preferably 1,1,3,3-tetramethylbutyl hydroperoxide, from the viewpoint of storage stability.

[0022] The oxidizing agent content 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 first and second liquids.

[0023] The reducing agent contained in the second solution may be, for example, a tertiary amine, a thiourea derivative, or a transition metal salt. Examples of tertiary amines include triethylamine, tripropylamine, tributylamine, and N,N-dimethylparatoluidine. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylenethiourea. Examples of transition metal salts include cobalt naphthenate, copper naphthenate, and vanadylacetylacetonate. The reducing agent can be used individually or in combination of two or more types.

[0024] 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, ethylenethiourea. From a similar viewpoint, the transition metal salt is preferably vanadylacetylacetonate.

[0025] 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 first liquid and the second liquid.

[0026] In the composition set, at least one of the first liquid and the second liquid contains a compound represented by the following formula (1).

Chemical formula

[0027] 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, both of R 11 and R 12 may be methyl groups.

[0028] The number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more. The composition of the present embodiment has a structure represented by formula (1) and contains a compound in which the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more, so that a cured product excellent in elongation at break can be formed while having low viscosity and excellent handleability. Further, in one embodiment, the cured product of this composition set 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.

[0029] In one embodiment, the polyoxyalkylene chain contains an oxyethylene group (in other words, a structural unit represented by the following formula (2)). This further suppresses the increase in viscosity of the composition (referring to one or both of the first and second liquids; the same applies hereinafter) while further increasing the strength of the cured product. [ka]

[0030] In this case, R 13 The group may be a divalent group having a polyoxyethylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formulas (1-2) (polyethylene glycol di(meth)acrylate). [ka] In formula (1-2), R 11 and R 12 R in equation (1) 11 and R 12 These are synonymous, and m is an integer greater than or equal to 100. m can take the same lower and upper limits as the number of oxyalkylene groups described above.

[0031] In another embodiment, the polyoxyalkylene chain includes an oxypropylene group (in other words, a structural unit represented by formula (3) below). This further facilitates the handling of the composition. [ka]

[0032] In this case, R 13 The group may be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formulas (1-3) (polypropylene glycol di(meth)acrylate). [ka] In formula (1-3), R 11 and R 12R in equation (1) 11 and R 12 These are equivalent to the above, where n is an integer greater than or equal to 100. m can take the same lower and upper limits as the number of oxyalkylene groups described above.

[0033] In another embodiment, the polyoxyalkylene chain is preferably a copolymer chain containing an oxyethylene group and an oxypropylene group, from the viewpoint of further facilitating the handling of the composition and the low elasticity, high elongation, and high strength of the cured product. The copolymer chain may be an alternating copolymer chain, a block copolymer chain, or a random copolymer chain. From the viewpoint of further facilitating the handling of the composition, the copolymer chain is preferably a random copolymer chain.

[0034] In each of the embodiments described above, the polyoxyalkylene chain may have, in addition to the oxyethylene group and the oxypropylene group, oxytetramethylene group, oxybutylene group, oxypentylene group, and other oxyalkylene groups having 4 to 5 carbon atoms as structural units.

[0035] R 13 In addition to the polyoxyalkylene chain described above, the group may be a divalent group further having other organic groups. The other organic groups may be chain-like groups other than the polyoxyalkylene chain, such as a methylene chain (a chain with -CH2- as a structural unit), a polyester chain (a chain containing -COO- as a structural unit), a polyurethane chain (a chain containing -OCON- as a structural unit), etc.

[0036] For example, the compound represented by formula (1) may also be a compound represented by the following formulas (1-4). [ka] In formula (1-4), R 11 and R 12 R in equation (1) 11 and R 12 These are synonymous, and R 14 and R 15Each of these is an alkylene group having 2 to 5 carbon atoms, k1 and k3 are each independent integers greater than or equal to 100, and k2 is an integer greater than or equal to 2.

[0037] k1 and k3 can independently take the same lower and upper limits as the number of oxyalkylene groups described above. k2 may be an integer less than or equal to 16, for example.

[0038] Multiple Rs exist 14 and R 15 Each of them may be identical to the others, or they may be different to each other. There are multiple R's. 14 and R 15 Each preferably contains an ethylene group and a propylene group. That is, (R 14 O) k1 Polyoxyalkylene chains represented by (R 15 O) k3 The polyoxyalkylene chains represented by are preferably copolymer chains containing an oxyethylene group and an oxypropylene group, respectively.

[0039] 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 of the cured product having lower elasticity and superior 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.

[0040] 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, even more preferably 300 Pa·s or less, and particularly preferably 200 Pa or less, from the viewpoint of further improving the handling 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.

[0041] The compound represented by formula (1) may be solid at 25°C. In this case, from the viewpoint of further improving the handling of the composition, the compound represented by formula (1) is preferably liquid at 50°C. Also in this case, from the viewpoint of further improving the handling of the composition, 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. 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.

[0042] Viscosity refers to the value measured according to JIS Z 8803, specifically the value measured using an E-type viscometer (for example, PE-80L manufactured by Toki Sangyo Co., Ltd.). The viscometer can be calibrated according to 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 compound.

[0043] The content of the compound represented by 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, 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, based on the total amount of the first liquid and the second liquid.

[0044] 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 less, 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, based on 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").

[0045] The composition may further contain other polymerizable compounds that can copolymerize with the compound represented by formula (1) described above, for the purpose of adjusting the physical properties of the composition.

[0046] 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 also be compounds having, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocyclic group, 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, the viscosity of the composition can be adjusted by including alkyl (meth)acrylates in the composition. Furthermore, the adhesion of the composition and its cured product to the member can be further improved by including compounds having a hydroxyl group, a carboxyl group, an amino group, or an epoxy group in addition to the (meth)acryloyl group.

[0047] The alkyl group (the alkyl group portion other than the (meth)acryloyl group) in alkyl (meth)acrylate may be linear, 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, and may also be 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0048] Examples of alkyl(meth)acrylates having a linear alkyl group include 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, which are alkyl(meth)acrylates having a linear alkyl group with 1 to 11 carbon atoms. Examples of alkyl(meth)acrylates having a linear alkyl group with 12 to 30 carbon atoms include syl(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, and octacosyl(meth)acrylate.

[0049] Examples of alkyl(meth)acrylates having branched alkyl groups include 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 other alkyl(meth)acrylates having branched alkyl groups with 1 to 11 carbon atoms, as well as isomiristyl Examples of alkyl(meth)acrylates having branched alkyl groups with 12 to 30 carbon atoms include 12-30 carbon atoms, such as 14-(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, and decyltetradecanyl(meth)acrylate.

[0050] 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, and dicyclopentanyl (meth)acrylate.

[0051] Examples of compounds having a (meth)acryloyl group and an aromatic hydrocarbon group include benzyl (meth)acrylate.

[0052] 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, and methoxypolybutylene glycol (meth)acrylate.

[0053] Examples of compounds having a (meth)acryloyl group and a heterocyclic group include tetrahydrofurfuryl (meth)acrylate.

[0054] Examples of compounds having a (meth)acryloyl group and an alkoxy group include 2-methoxyethyl acrylate.

[0055] Examples of compounds having a (meth)acryloyl group and a phenoxy group include phenoxyethyl (meth)acrylate.

[0056] Examples of compounds having groups containing a (meth)acryloyl group and a silane group include 3-acryloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, and 10-acryloyloxydecyltriethoxysilane.

[0057] Examples of compounds having a (meth)acryloyl group and a group containing a siloxane bond include silicone (meth)acrylates.

[0058] 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, perfluoro Examples include (meth)acrylates containing a fluorine atom, such as tridecylmethyl (meth)acrylate, 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.

[0059] Examples of compounds 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, and 12-hydroxylauryl (meth)acrylate; and hydroxyalkylcycloalkane (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.

[0060] Examples of compounds having a (meth)acryloyl group and a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, monohydroxyethyl phthalate acrylate (e.g., "Aronics M5400" manufactured by Toagosei Co., Ltd.), and 2-acryloyloxyethyl succinate (e.g., "NK Ester A-SA" manufactured by Shin Nakamura Chemical Co., Ltd.).

[0061] Examples of compounds having a (meth)acryloyl group and an amino group include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate.

[0062] Examples of compounds having a (meth)acryloyl group and an epoxy group include glycidyl (meth)acrylate, α-ethyl(meth)acrylate, α-n-propyl(meth)acrylate, α-n-butyl(meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 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 (meth)acrylate, and α-ethyl(meth)acrylate-β-methylglycidyl.

[0063] 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, 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, based on the total amount of the first liquid and the second liquid.

[0064] 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, 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, based on 100 parts by mass of the total content of polymerizable components.

[0065] The composition may further contain an antioxidant from the viewpoint of improving the thermal reliability of the cured product of the composition set. The antioxidant may be, for example, a phenolic antioxidant, a benzophenone antioxidant, a benzoate antioxidant, a hindered amine antioxidant, a benzotriazole antioxidant, etc., and is preferably a phenolic antioxidant.

[0066] Phenolic antioxidants, for example, have 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. 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.

[0067] The antioxidant content may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, based on the total amount of the first and second liquids, and may be 5% by mass or less, 4% by mass or less, 3% by mass or less, 2% by mass or less, or 1% by mass or less.

[0068] The composition may further 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, colorants, nucleating agents, heat stabilizers, foaming agents, flame retardants, vibration dampers, dehydrating agents, and flame retardant aids (e.g., metal oxides). The content of other additives may be 0.1% by mass or more and 30% by mass or less, based on the total amount of the first and second liquids.

[0069] In the composition set, it is preferable that each component other than the oxidizing agent and the reducing agent is included in both the first and second liquids. That is, in one embodiment, it is preferable that the first liquid contains an oxidizing agent and a compound represented by formula (1) (and other components used as needed), and the second liquid contains a reducing agent and a compound represented by formula (1) (and other components used as needed).

[0070] The first and second liquids in the above-described composition set have low viscosity, yet their cured products exhibit low elasticity, high elongation, and high strength, making them suitable for applications such as thermal conductive materials (also called heat dissipation materials), adhesives, structural adhesives, battery binders, stress relievers, sealants, coatings, and paints. Similarly, the cured products of the above-described composition set exhibit low elasticity, high elongation, and high strength, making them suitable for each of the above-mentioned applications. [Examples]

[0071] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0072] In the examples, the following components were used as common components for the first and second solutions. (A-1) A mixture of compounds represented by formula (1-7) synthesized by the procedure shown below (weight-average molecular weight: 15000, where m1+m2 in formula (1-7) is approximately 252±5 and n1+n2 is approximately 63±5 integers (where m1, m2, n1, and n2 are each independently integers of 2 or more, m1+n1≧100, m2+n2≧100), viscosity at 25℃: 50 Pa·s) [ka] In equations (1-7), -r- is a sign representing random copolymerization. (A-2) Compounds 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 approximately an integer of 105±5, viscosity at 25℃: 55 Pa·s) [ka] In equations (1-8), -r- is a sign representing random copolymerization.

[0073] (B-1)2-Ethylhexylacrylate (manufactured by Nippon Shokubai Co., Ltd.) (B-2) 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) (B-3) Isodecyl acrylate (Hitachi Chemical Co., Ltd. "FA111A")

[0074] [Synthesis of compounds represented by formulas (1-7)] A 500 mL flask, consisting of a stirrer, thermometer, nitrogen gas inlet tube, outlet tube, and heating jacket, was used as the reactor. 225 g of glycol having polyoxyalkylene chains (Sanyo Chemical Industries, Ltd. "Newpol 75H-90000") and 300 g of toluene were added to the reactor and stirred at 45°C and a stirring speed of 250 revolutions / minute. Nitrogen was supplied at 100 mL / min and stirred for 30 minutes. The mixture was then cooled to 25°C, and after cooling was complete, 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. The temperature was then raised to 45°C and the reaction was carried out for 2 hours. The reaction mixture was filtered, and the filtrate was desoluble to obtain the compound represented by formula (1-7).

[0075] [Synthesis of compounds represented by formulas (1-8)] The compound represented by formula (1-8) was obtained by the same method as in the synthesis method of the compound represented by formula (1-7), except that the glycol having a polyoxyalkylene chain ("Newpol 75H-90000" manufactured by Sanyo Chemical Industries, Ltd.) was replaced with 240 g of polyoxyethylene polyoxypropylene glycol (molecular weight 16000).

[0076] [Preparation of composition set] The common components and an oxidizing agent (oxidizing agent 1: cumene hydroperoxide (containing approximately 20% aromatic hydrocarbons) (Tokyo Chemical Industries, Ltd.), or oxidizing agent 2: 1,1,3,3-tetramethylbutyl hydroperoxide (Trigonox TMBH-L, manufactured by Kayaku Nurion Co., Ltd.)) were mixed in the amounts (parts by mass) shown in Table 1 to obtain the first solution. The common components and a reducing agent (ethylenethiourea) were also mixed in the amounts (parts by mass) shown in Table 1 to obtain the second solution. Note that the amounts of the common components shown in Table 1 are the amounts used in the first and second solutions, respectively.

[0077] [Measurement of elongation at break, strength at break, and tensile modulus] The first and second liquids were mixed in the mass ratio shown in Table 1 to obtain a mixture of the first and second liquids. Next, each of these mixtures was filled into a 10cm × 10cm × 0.2mm mold (made of SUS plate), and after covering it with a SUS plate, it was heated at 135°C for 15 minutes to cure, thereby obtaining a cured product of the composition set with a thickness of 0.2mm (cured product of the mixture of the first and second liquids). The elongation at break, tensile modulus, and breaking strength of each cured product at 25°C were measured using a tensile testing machine ("Autograph EZ-TEST EZ-S" manufactured by Shimadzu Corporation). For the measurement, a cured product with a shape of 0.2mm (film thickness) × 5mm (width) × 30mm (length) was measured according to JIS K7161 under the conditions of a chuck distance of 20mm and a tensile speed of 5mm / min.

[0078] [Table 1]

[0079] As described above, components (A-1) to (A-2) used in Examples 1 to 5 have low viscosity at 25°C, and therefore the composition sets (first liquid and second liquid) containing them were easy to handle. Furthermore, the cured products of these composition sets showed a high elongation at break.

Claims

[Claim 1] A composition set 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 following formula (1): 【Chemistry 1】 [In formula (1), R １１ and R １２ Each of these independently represents a hydrogen atom or a methyl group, R １３ This represents a divalent group having a polyoxyalkylene chain. A composition set wherein the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more.

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