Curable composition, heat-accumulating material, and article

Abstract

A curable composition containing: a compound represented by the following formula (1), and at least one polyalkylene glycol ether selected from the group consisting of polyalkylene glycol monoethers and polyalkylene glycol diethers. 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.

Description

Technical Field

[0001] This invention relates to a curable composition, a heat storage material, and an article. Background Technology

[0002] Thermal storage materials are materials that can extract stored energy as heat as needed. These materials are used in air conditioning equipment, underfloor heating systems, refrigerators, electronic components such as IC chips, automotive interior and exterior trim materials, automotive parts such as carbon canisters, and insulated containers.

[0003] As a method of heat storage, latent heat storage, which utilizes the phase change of a substance, is widely used from the perspective of the amount of heat. For example, Patent Document 1 discloses a heat storage material composition containing polyalkylene glycol as a latent heat storage component.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Application Publication No. 2006-96898 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] According to the research conducted by the present invention, there is room for further improvement in the reliability of heat storage materials containing polyalkylene glycols under high temperature and high humidity environments. Therefore, in one aspect, an object of the present invention is to provide a curable composition capable of forming a heat storage material with excellent reliability under high temperature and high humidity environments.

[0009] means for solving technical problems

[0010] The inventors conducted intensive research and found that by combining a specific compound having a polyoxyalkylene chain and having two (meth)acryloyl groups with a compound formed by etherifying the terminal hydroxyl group of at least one of a polyalkylene glycol, a heat storage material with excellent reliability under high temperature and high humidity conditions can be formed, thus completing the present invention. In some aspects, the present invention provides the following [1] to [8].

[0011] [1] A curable composition comprising: a compound represented by the following formula (1); and at least one polyalkylene glycol ether selected from the group consisting of polyalkylene glycol monoethers and polyalkylene glycol diethers.

[0012]

[0013] In equation (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R13 This indicates a divalent group having a polyoxyalkylene chain.

[0014] [2] The curable composition according to [1] contains a compound represented by formula (1) having a weight average molecular weight of 1000 or more as the compound represented by formula (1).

[0015] [3] The curable composition according to [1] or [2] contains a polyalkylene glycol ether having a weight-average molecular weight of 400 or more as the polyalkylene glycol ether.

[0016] [4] The curable composition according to any one of [1] to [3] contains a polyalkylene glycol ether having a weight average molecular weight of less than 5,000 as the polyalkylene glycol ether.

[0017] [5] The curable composition according to any one of [1] to [4] further contains a compound represented by the following formula (3).

[0018]

[0019] In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 This indicates a monovalent group having a polyoxyalkylene chain.

[0020] [6] The curable composition according to any one of [1] to [5] is used for the formation of a heat storage material.

[0021] [7] A heat storage material comprising a cured product of any one of [1] to [6].

[0022] [8] An article comprising: a heat source; and a cured product of any one of [1] to [6] of a curable composition disposed in thermal contact with the heat source.

[0023] Invention Effects

[0024] According to one aspect of the present invention, a curable composition capable of forming a heat storage material with excellent reliability under high temperature and high humidity conditions can be provided. Attached Figure Description

[0025] Figure 1 This is a schematic cross-sectional view illustrating one embodiment of the heat storage material.

[0026] Figure 2 It is a schematic cross-sectional view showing one embodiment of an article and its manufacturing method.

[0027] Figure 3 This is a schematic cross-sectional view showing another embodiment of the article.

[0028] Figure 4 This is a schematic cross-sectional view illustrating another embodiment of the method for manufacturing the article. Detailed Implementation

[0029] Hereinafter, embodiments of the present invention will be described in detail with appropriate reference to the accompanying drawings. However, the present invention is not limited to these embodiments.

[0030] In this specification, "(meth)acryloyl" refers to "acryloyl" and its corresponding "methacryloyl", and the same applies to similar expressions such as "(meth)acrylate" and "(meth)acrylic acid".

[0031] The weight-average molecular weight (Mw) in this specification was determined using gel permeation chromatography (GPC) under the following conditions, and refers to the value determined using polystyrene as a standard.

[0032] • Measuring equipment: HLC-8320GPC (product name, manufactured by TOSOH CORPORATION)

[0033] • Analytical column: TSKgel SuperMultipore HZ-H (connected to 3 columns) (Product name, manufactured by TOSOHCORPORATION)

[0034] • Guard column: TSKguardcolumn SuperMP(HZ)-H (Product name, manufactured by TOSOH CORPORATION)

[0035] • Elution buffer: THF

[0036] • Measurement temperature: 25℃

[0037] [Curing composition]

[0038] One embodiment of the curable composition contains a compound represented by the following formula (1); and at least one polyalkylene glycol ether selected from the group consisting of polyalkylene glycol monoethers and polyalkylene glycol diethers.

[0039]

[0040] In equation (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 13 This indicates a divalent group having a polyoxyalkylene chain.

[0041] In one implementation, R can be 11 and R 12One of them is a hydrogen atom and the other is a methyl group; in another embodiment, it can be R. 11 and R 12 These two are hydrogen atoms, and in another embodiment, they can be R. 11 and R 12 Both of these are methyl groups.

[0042] Polyoxyalkylene chains are represented, for example, by the following formula (1-1).

[0043]

[0044] In equation (1-1), R 14 The symbol indicates an alkylene group, m represents an integer greater than 2, and * represents a bonded bond.

[0045] R 14 The alkylene groups represented can be linear or branched. R 14 For example, it can be an alkylene group with 2 to 4 carbon atoms. Multiple R groups exist in the polyoxyalkylene chain. 14 They can be the same as each other or different from each other. Multiple Rs exist in the polyoxyalkylene chain. 14 Preferably, it is selected from one or more of the group consisting of ethylene, propylene, and butylene; more preferably, it is selected from one or two of the group consisting of ethylene and propylene; and even more preferably, it is entirely composed of ethylene.

[0046] m can be an integer of 10 or more, or 20 or more, or an integer of 300 or less, 250 or less, or 200 or less. m can be an integer of the molecular weight of the compound represented by formula (1), for example, 1000 or more. From the viewpoint of obtaining a heat storage material with better reliability under high temperature and high humidity conditions, it is preferable that the molecular weight of the compound represented by formula (1) is an integer of 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, or 7000 or more. From the viewpoint of suppressing the decrease in heat storage characteristics caused by overcooling, m is preferably an integer of the molecular weight of the compound represented by formula (1), which is 12000 or less, 11000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, or 4000 or less, 3000 or less, or 2000 or less.

[0047] R 13 It can also be a divalent group that has other organic groups besides the polyoxyalkylene chain. Other organic groups can be chain-like groups other than the polyoxyalkylene chain, such as methylene chains (chains with -CH2- as structural units), polyester chains (chains containing -COO- in structural units), polyurethane chains (chains containing -OCON- in structural units), etc.

[0048] The compound represented by formula (1) is preferably the compound represented by the following formula (1-2).

[0049]

[0050] In equation (1-2), R 11 and R 12 respectively with R in equation (1) 11 and R 12 The meaning is the same, R 14 and m are respectively related to R in equation (1-1) 14 The meanings of "and m" are the same.

[0051] The weight-average molecular weight (Mw) of the compound represented by formula (1) can be, for example, 1000 or more. From the viewpoint of obtaining a heat storage material with better reliability under high temperature and high humidity conditions, it is preferably 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, or 7000 or more. From the viewpoint of suppressing the reduction of heat storage characteristics caused by supercooling, the weight-average molecular weight (Mw) of the compound represented by formula (1) is preferably 12000 or less, 11000 or less, 10000 or less, 9000 or less, 8000 or less, 7000 or less, 6000 or less, 5000 or less, or 4000 or less, 3000 or less, or 2000 or less.

[0052] The curable composition may contain one compound represented by formula (1) having the above-mentioned Mw, or two or more compounds represented by formula (1) having different Mws. In the latter case, if the Mw of the compound represented by formula (1) is determined by the above method, two or more peaks corresponding to the Mw of each of the two or more compounds represented by formula (1) are observed in the obtained molecular weight distribution.

[0053] In one embodiment, from the viewpoint of obtaining a heat storage material with superior heat storage capacity, the curable composition preferably contains at least one compound having a Mw of 2000 or more (referred to as compound (1A)), and may also contain at least one compound (1A) and at least one compound represented by formula (1) having a Mw of less than 2000 (referred to as compound (1B)). The Mw of compound (1A) is more preferably 3000 or more, 4000 or more, 5000 or more, 6000 or more, or 7000 or more, and for example, 12000 or less, 11000 or less, or 10000 or less. The Mw of compound (1B) may, for example, be 1000 or more, or 1500 or less.

[0054] Based on the total amount of the curable composition, the content of the compound represented by formula (1) can be, for example, 1% by mass or more, 2% by mass or more, or 5% by mass or more. From the viewpoint that the cured product of the curable composition has excellent flexibility and can obtain a heat storage material with better heat storage capacity, it is preferable to be 10% by mass or more, 15% by mass or more, or 20% by mass or more, and more preferably 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. In addition, if the cured product of the curable composition has excellent flexibility, it can be used by bending, for example, so the cured product is more preferably used as a heat storage material that can be applied to a wider range of uses. Based on the total amount of the curable composition, the content of the compound represented by formula (1) can be, for example, 99% by mass or less, 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less. When the curable composition contains two or more compounds represented by formula (1), the total amount of these compounds can be within the above range. When the curable composition contains the above-mentioned compound (1A) and / or the above-mentioned compound (1B), the total amount of compound (1A) and compound (1B) can be within the above-mentioned range, and the content of each of compound (1A) and compound (1B) can be within the above-mentioned range.

[0055] When the curable composition contains, in addition to the compound represented by formula (1), a compound that can copolymerize with the compound represented by formula (1) (details will be described later), the content of the compound represented by formula (1) can be 1 part by mass or more, 2 parts by mass or more, or 5 parts by mass or more, relative to 100 parts by mass of the total content of the compound represented by formula (1) and the total content of the compound that can copolymerize with the compound represented by formula (1) (hereinafter referred to as "the total content of the polymerizable component"). From the viewpoint that the cured product of the curable composition has excellent flexibility and can obtain a heat storage material with better heat storage, it is preferred to be 10 parts by mass or more or 15 parts by mass or more, more preferably 20 parts by mass or more, 25 parts by mass or more, 30 parts by mass or more or 35 parts by mass or more, and even more preferably 40 parts by mass or more. The content of the compound represented by formula (1) can be, for example, 99 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, or 50 parts by mass or less, relative to the total 100 parts by mass of the polymeric component.

[0056] Polyalkylene glycol ethers are represented, for example, by the following formula (2).

[0057]

[0058] In equation (2), R 21 and R 22 Each can independently represent a hydrogen atom or a monovalent hydrocarbon group, R23 This indicates an alkylene group, and n represents an integer greater than or equal to 2. Where R... 21 and R 22 At least one of them represents a monovalent hydrocarbon group. In R 21 and R 22 When only one of the groups is a monovalent hydrocarbon group, the polyalkylene glycol ether is a polyalkylene glycol monoether. In R 21 and R 22 When both of these are monovalent hydrocarbon groups, the polyalkylene glycol ether is a polyalkylene glycol diether.

[0059] R 21 and R 22 The monovalent hydrocarbon group represented can be, for example, an alkyl or an aryl group, preferably an alkyl group. The alkyl group can be straight-chain or branched. The number of carbon atoms in the alkyl group can be, for example, 1 or more, or 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less. As an aryl group, phenyl can be cited as an example.

[0060] R 23 The alkylene groups represented can be linear or branched; from the viewpoint of obtaining heat storage materials with superior heat storage capacity, linear formation is preferred. 23 For example, it can be an alkylene group with 2 to 4 carbon atoms. Multiple R groups exist in one molecule. 23 They can be the same or different from each other. A single molecule contains multiple R's. 23 Preferably, all of them are ethylene.

[0061] In one embodiment, R is preferred. 21 and R 22 The monovalent hydrocarbon group represented is an alkyl group and R 23 All alkylene groups referred to are ethylenes. That is, the polyalkylene glycol ethers are preferably at least one selected from the group consisting of polyethylene glycol monoalkyl ethers and polyethylene glycol dialkyl ethers.

[0062] n can be an integer of 10 or more or 20 or more, or an integer of 100 or less, 90 or less, 80 or less, 70 or less, or 60 or less. n can be an integer whose molecular weight is 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, or 1000 or more. From the viewpoint of further increasing the reliability improvement effect under high temperature and high humidity conditions by etherifying the terminal hydroxyl groups of polyalkylene glycols, n is preferably an integer whose molecular weight is 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0063] The weight-average molecular weight (Mw) of the compound represented by formula (2) can be, for example, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, or 1000 or more. From the viewpoint of further increasing the reliability improvement effect under high temperature and high humidity conditions by etherifying the terminal hydroxyl groups of the polyalkylene glycol, the weight-average molecular weight (Mw) of the compound represented by formula (2) is preferably 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0064] Based on the total amount of the curable composition, the content of polyalkylene glycol ether can be, for example, 10% by mass or more. From the viewpoint of obtaining a heat storage material with superior heat storage capacity, it is preferably 15% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more. Based on the total amount of the curable composition, the content of polyalkylene glycol ether can be, for example, 80% by mass or less, 70% by mass or less, 65% by mass or less, or 60% by mass or less.

[0065] The content of polyalkylene glycol ether can be 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, relative to the total 100 parts by mass of the polymerizable components. From the viewpoint of obtaining a heat storage material with superior heat storage capacity, it is preferable to have 40 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 60 parts by mass or more. It can also be 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, or 100 parts by mass or more. The content of polyalkylene glycol can be 500 parts by mass or less, 400 parts by mass or less, 300 parts by mass or less, 200 parts by mass or less, 150 parts by mass or less, 120 parts by mass or less, 110 parts by mass or less, or 100 parts by mass or less, relative to the total 100 parts by mass of the polymerizable components.

[0066] The curable composition may also contain a polymerization initiator. There are no particular limitations on whether the polymerization initiator is a compound capable of initiating the polymerization of the compound represented by formula (1) and, as needed, a compound capable of copolymerizing with the compound represented by formula (1) (details are described later). For example, the polymerization initiator may be a thermal polymerization initiator that generates free radicals by heat, a photopolymerization initiator that generates free radicals by light, etc.

[0067] When the curable composition contains a thermal polymerization initiator, a cured product of the curable composition can be obtained by applying heat to the curable composition. In this case, the curable composition can be a curable composition that is cured by heating, preferably at 105°C or higher, more preferably at 110°C or higher, and even more preferably at 115°C or higher, or it can be a curable composition that is cured by heating, for example, at 200°C or lower, 190°C or lower, or 180°C or lower. The heating time when heating the curable composition can be suitably selected according to the composition of the curable composition to ensure that the curable composition is properly cured.

[0068] Examples of thermal polymerization initiators include: azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylpentanonitrile, azobiscyclohexanone-1-carboxynitrile, azobisbenzoyl and other azo compounds, benzoyl peroxide, lauroyl peroxide, di-tert-butylperoxide-6-tert-phthalic acid ester, tert-butylperoxide-2-ethylhexanoate, 1,1-tert-butylperoxide-3,3,5-trimethylcyclohexane, tert-butylperoxyisopropyl carbonate and other organic peroxides. One of these initiators can be used alone or in combination of two or more.

[0069] When the curable composition contains a photopolymerization initiator, a cured product of the curable composition can be obtained, for example, by irradiating the curable composition with light (e.g., light containing at least a portion of wavelengths from 200 nm to 400 nm (ultraviolet light)). The light irradiation conditions can be appropriately set depending on the type of polymerization initiator.

[0070] Photopolymerization initiators can be, for example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-keto alcohol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzyl-based photopolymerization initiators, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, etc.

[0071] 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 (trade name: Omnirad 651, manufactured by IGM Resins BV), and anethole methyl ether. Examples of acetophenone-based photopolymerization initiators include: 1-hydroxycyclohexylphenyl ketone (trade name: Omnirad 184, manufactured by IGM Resins BV), 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (trade name: Omnirad 2959, manufactured by IGM Resins BV), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (trade name: Omnirad 1173, manufactured by IGM Resins BV), and methoxyacetophenone.

[0072] Examples of α-ketool-based photopolymerization initiators include 2-methyl-2-hydroxyphenylacetone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropane-1-one. Examples of aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride. Examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

[0073] Examples of benzoin-based photopolymerization initiators include benzoin itself. Examples of benzyl-based photopolymerization initiators include benzyl groups. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyethylene benzophenone, and α-hydroxycyclohexylphenyl ketone. Examples of benzyl dimethyl ketal are ketal-based photopolymerization initiators. Examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0074] Examples of acylphosphine oxide photopolymerization initiators include: bis(2,6-dimethoxybenzoyl)phosphine 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)-tert-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, and bis(2-methoxybenzoyl)cyclohexylphosphine oxide. Benzoyl)(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-di- Methoxybenzoyl)-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-diisopropylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphosphine oxide, bis(2 Phosphorus oxychloride (2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine 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)phosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tris(2-methylbenzoyl)phosphine oxide, etc.

[0075] The aforementioned photopolymerization initiators can be used alone or in combination of two or more.

[0076] From the viewpoint of suitable polymerization, 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, relative to the total content of the polymerizable components (100 parts by mass). From the viewpoint that the molecular weight of the polymer in the cured product of the curable composition is within a suitable range and that decomposition products are suppressed, thus achieving suitable adhesive strength when used as a heat storage material, the 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, relative to the content of the polymerizable components (100 parts by mass).

[0077] The curable composition may further contain a compound capable of copolymerizing with the compound represented by formula (1). This copolymerizable compound may, for example, have a group containing an olefinically unsaturated bond (olefinically unsaturated group). Examples of olefinically unsaturated groups include (meth)acryloyl, vinyl, allyl, etc. The copolymerizable compound is preferably a compound having a (meth)acryloyl group.

[0078] From the viewpoint that a heat storage material with superior heat storage capacity can be obtained, the curable composition preferably also contains the compound represented by the following formula (3) as the copolymerizable compound.

[0079]

[0080] In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 This indicates a monovalent group having a polyoxyalkylene chain.

[0081] R 32 For example, it can be a group represented by the following formula (3-1).

[0082]

[0083] In equation (3-1), R 33 R represents an alkylene group. 34 This indicates a hydrogen atom or an alkyl group, p represents an integer greater than 2, and * represents a bond.

[0084] R 33 The alkylene groups represented can be linear or branched; from the viewpoint of obtaining heat storage materials with superior heat storage capacity, linear formation is preferred. 33 For example, it can be an alkylene group with 2 to 4 carbon atoms. Multiple R groups exist in the polyoxyalkylene chain. 33They can be the same as each other or different from each other. The polyoxyalkylene chain is preferably one or more of the group consisting of oxyethylene, oxypropylene and oxybutylene, more preferably one or two of the group consisting of oxyethylene and oxypropylene, and even more preferably only oxyethylene.

[0085] R 34 The alkyl group can be linear or branched; from the viewpoint of obtaining a heat storage material with superior heat storage capacity, a linear form is preferred. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5. 34 Hydrogen atoms or methyl groups are particularly preferred.

[0086] p can be an integer of 10 or more, or 20 or more, or an integer of 80 or less, 70 or less, or 60 or less. From the viewpoint of obtaining a heat storage material with superior heat storage capacity, p is preferably an integer whose molecular weight of the compound represented by formula (3) is 800 or more, 900 or more, or 1000 or more, and more preferably an integer whose molecular weight of the compound represented by formula (3) is 1200 or more, 1400 or more, 1600 or more, 1800 or more, or 2000 or more. p can also be an integer whose molecular weight of the compound represented by formula (3) is 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0087] From the viewpoint of obtaining a heat storage material with superior heat storage capacity, the weight-average molecular weight (Mw) of the compound represented by formula (3) is preferably 800 or more, 900 or more, or 1000 or more, and more preferably 1200 or more, 1400 or more, 1600 or more, 1800 or more, or 2000 or more. The weight-average molecular weight (Mw) of the compound represented by formula (3) may also be 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0088] The content of the compound represented by formula (3) can be, for example, 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more, relative to the total 100 parts by mass of the polymerizable components. From the viewpoint of obtaining a heat storage material with superior heat storage capacity, it is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 60 parts by mass or more, and particularly preferably 70 parts by mass or more. The content of the compound represented by formula (3) can be, for example, 98 parts by mass or less, 90 parts by mass or less, or 80 parts by mass or less, relative to the total 100 parts by mass of the polymerizable components.

[0089] When the curable composition contains a compound represented by formula (3), from the viewpoint that the cured product of the curable composition can be suitably used as a heat storage material, the melting point of the compound represented by formula (3) is preferably close to the melting point of the polyalkylene glycol ether. The absolute value of the difference between the melting point of the compound represented by formula (3) and the melting point of the polyalkylene glycol ether is preferably 20°C or less, more preferably 15°C or less, and even more preferably 10°C or less.

[0090] The melting points of the compounds represented by formula (3) and the polyalkylene glycol ethers were determined as follows. Using a differential scanning calorimeter (e.g., DiscoveryDSC250 manufactured by TA Instruments Japan Inc.), the temperature was increased to 100°C at a rate of 20°C / min, held at 100°C for 3 minutes, then decreased to -20°C at a rate of 3°C / min, and then held at -20°C for 3 minutes before being increased back to 100°C at a rate of 3°C / min.

[0091] From the viewpoint of adjusting the hardness of the cured product of the curing composition and from the viewpoint that the polymerization initiator is easy to dissolve in the curing composition when it is a solid, the curing composition may also contain the compound represented by the following formula (4) as a compound that can copolymerize with the compound represented by formula (1).

[0092]

[0093] In equation (4), R 41 R represents a hydrogen atom or a methyl group. 42 Indicates alkyl group.

[0094] R 42 The alkyl group can be linear or branched; from the viewpoint of obtaining a heat storage material with superior heat storage capacity, a linear form is preferred. The number of carbon atoms in the alkyl group can be, for example, 1 to 30. The number of carbon atoms in the alkyl group can be 1 to 11, 1 to 8, 1 to 6, or 1 to 4, or it can be 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0095] The content of the compound represented by formula (4) can be, for example, more than 0.5 parts by mass, more than 1 part by mass, or more than 1.5 parts by mass, or less than 10 parts by mass, less than 8 parts by mass, or less than 6 parts by mass, relative to the total content of the polymeric components of 100 parts by mass.

[0096] The curable composition may also contain a compound represented by formula (5) as a compound capable of copolymerizing with the compound represented by formula (1).

[0097]

[0098] In equation (5), R 51 R represents a hydrogen atom or a methyl group. 52 This indicates a monovalent group that has a reactive group.

[0099] When the curable composition also contains the compound represented by formula (5), after the compound represented by formula (1) and the compound represented by formula (5) (and other compounds that can copolymerize with the compound represented by formula (1)) are polymerized, the reactive groups contained in the compound represented by formula (5) react with the curing agent described later, thereby enabling the curable composition to be further cured.

[0100] R 52 The reactive group represented is a group capable of reacting with the curing agent described later, such as at least one group selected from the group consisting of carboxyl, hydroxyl, isocyanate, amino, and epoxy groups. That is, the compound represented by formula (5) is, for example, a carboxyl-containing compound, a hydroxyl-containing compound, an isocyanate-containing compound, an amino-containing compound, or an epoxy-containing compound.

[0101] Examples of carboxyl-containing compounds include: (meth)acrylic acid, (meth)acrylic acid carboxyethyl ester, (meth)acrylic acid carboxypentyl ester, itaconic acid, maleic acid, fumaric acid, butenoic acid, isobutenoic acid, etc.

[0102] Examples of hydroxyl-containing compounds include: 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylaurate (meth)acrylate, and other hydroxyalkyl (meth)acrylate esters; methyl (4-hydroxymethylcyclohexyl)methacrylate and other hydroxyalkylcycloene (meth)acrylate esters. Hydroxyl-containing compounds can also include hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, etc.

[0103] Examples of compounds containing isocyanate groups include 2-methacryloyloxyethyl isocyanate and 2-acryloyloxyethyl isocyanate.

[0104] The isocyanate group in compounds containing isocyanate groups can also be blocked (protected) by a blocking agent (protecting group) that can be deactivated by heat. That is, compounds containing isocyanate groups can also be compounds with block isocyanate groups as represented by the following formula (5-1).

[0105]

[0106] In the formula, B represents the protecting group, and * represents the bonding bond.

[0107] The protecting group in the block isocyanate group can also be a protecting group that can be deprotected by heating (e.g., heating to 80°C–160°C). In the block isocyanate group, under deprotection conditions (e.g., heating to 80°C–160°C), a displacement reaction between the blocking agent (protecting group) and the curing agent described later can occur. Alternatively, in the block isocyanate group, an isocyanate group is generated through deprotection, and the isocyanate group can also react with the curing agent described later.

[0108] Examples of blocking agents in block isocyanate groups include: oxime compounds such as formaldehyde oxime, acetaldehyde oxime, acetyl oxime, methyl ethyl ketone oxime, and cyclohexanone oxime; pyrazole compounds such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole; lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; thiols such as thiophenol, methyl thiophenol, and ethyl thiophenol; acid amide compounds such as acetamide and benzamide; and imide compounds such as succinic imide and maleic imide.

[0109] Examples of compounds having block isocyanate groups include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and 2-(O-[1'-methylpropyleneamino]carboxylamino)methacrylate.

[0110] Examples of amino-containing compounds include, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, etc.

[0111] Examples of epoxy-containing compounds include: glycidyl (meth)acrylate, α-ethyl (meth)acrylate, α-n-propyl (meth)acrylate, α-n-butyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, 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, and α-ethyl (meth)acrylate, β-methylglycidyl (meth)acrylate.

[0112] The content of the compound represented by formula (5) can be, for example, more than 0.5 parts by mass, more than 1 part by mass, or more than 1.5 parts by mass, or less than 10 parts by mass, less than 8 parts by mass, or less than 5 parts by mass, relative to the total content of the polymeric components.

[0113] Based on the total amount of the curable composition, the total content of polymeric components can be 30% or more by mass, 40% or more by mass, or 50% or more by mass, or less than 99% by mass, less than 90% by mass, less than 80% by mass, less than 70% by mass, less than 60% by mass, or less than 50% by mass.

[0114] The compound represented by formula (1) and the compound that can copolymerize with the compound represented by formula (1) can be selected in such a way that the crosslinking density index calculated according to formula (A) below falls within the range described below.

[0115] Crosslinking density index = M / C × 1000…(A)

[0116] In the formula, M represents the total number of moles of polymerizable groups (olefinic unsaturated groups) in the polymerizable component (unit: moles), and C represents the total content of the polymerizable component (unit: g).

[0117] The crosslinking density index can be, for example, 2.5 or less. From the viewpoint of obtaining a heat storage material with better reliability under high temperature and high humidity environments, it is preferable to have a crosslinking density index of 2.0 or less, 1.8 or less, 1.6 or less, 1.4 or less, 1.2 or less, 1.0 or less, 0.8 or less, 0.6 or less, 0.5 or less, 0.4 or less, or 0.3 or less. The crosslinking density index can be, for example, 0.1 or more, 0.2 or more, or 0.3 or more.

[0118] When the curable composition contains a compound represented by formula (5), the curable composition preferably also contains a curing agent. The curing agent is a compound capable of reacting with the reactive groups contained in the compound represented by formula (5).

[0119] Examples of curing agents include isocyanate-based curing agents, phenol-based curing agents, amine-based curing agents, imidazole-based curing agents, acid anhydride-based curing agents, and carboxylic acid-based curing agents. These curing agents can be selected individually or in combination of two or more, depending on the type of reactive groups contained in the compound represented by formula (5). For example, when the reactive group is an epoxy group, a phenol-based curing agent or an imidazole-based curing agent is preferred.

[0120] Examples of isocyanate-based curing agents include: toluene diisocyanate (2,4-toluene diisocyanate or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m-phenylene diisocyanate or p-phenylene diisocyanate or mixtures thereof), 4,4'-diphenylene diisocyanate, 1,5-naphthalene diisocyanate (NDI), and diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate or 2,2'-diphenylmethane diisocyanate or mixtures thereof). Aromatic diisocyanates include methyl diisocyanate (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylene diisocyanate (1,3-xylene diisocyanate or 1,4-xylene diisocyanate or mixtures thereof) (XDI), tetramethylxylene diisocyanate (1,3-tetramethylxylene diisocyanate or 1,4-tetramethylxylene diisocyanate or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, etc.

[0121] Examples of isocyanate-based curing agents include: trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4-trimethylhexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, methyl hexanoate of 2,6-diisocyanate, and other aliphatic diisocyanates; 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanomethyl-3,5,5-trimethyl Cyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-methylene bis(cyclohexyl isocyanate), 2,4'-methylene bis(cyclohexyl isocyanate) or 2,2'-methylene bis(cyclohexyl isocyanate)), the trans, trans, trans, cis, cis, cis, or mixtures thereof (H12MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis(isocyanomethyl)cyclohexane (1,3-bis(isocyanomethyl)cyclohexane or 1,4-bis(isocyanomethyl)cyclohexane or mixtures thereof) (H6XDI), and other alicyclic diisocyanates.

[0122] Examples of phenolic curing agents include: bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S, tetramethyl-4,4'-biphenylphenol, dimethyl-4,4'-biphenylphenol, 1-(4-hydroxyphenyl)-2-[4-(1,1-bis-(4-hydroxyphenyl)ethyl)phenyl]propane, 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), trihydroxyphenylmethane, resorcinol, and hydroquinone. Phenolic varnishes include: pyrogallol; phenolic compounds with a diisopropylidene skeleton; phenolic compounds with a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; cresol compounds; ethylphenol compounds; butylphenol compounds; octylphenol compounds; phenolic varnish resins made from various phenols such as bisphenol A, bisphenol F, bisphenol S, and naphthol compounds; phenolic varnish resins containing a xylene-methylidene skeleton; phenolic varnish resins containing a dicyclopentadiene skeleton; phenolic varnish resins containing a biphenyl skeleton; phenolic varnish resins containing a fluorene skeleton; and phenolic varnish resins containing a furan skeleton.

[0123] Examples of amine-based curing agents include: aromatic amines such as diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, and m-xylylenediamine; aliphatic amines such as ethylenediamine, diethylenediamine, hexamethylenediamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, and polyetherdiamine; and guanidine compounds such as dicyandiamide and 1-(o-tolyl)biguanide.

[0124] Examples of imidazole-based curing agents include: 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-benzyl-2-methylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 2,3-dihydro-1H-pyrrole-[1,2-a]benzimidazole, 2,4-diamino-6(2'-methylimidazolium(1'))ethyl-triazine, 2 ,4-Diamino-6(2'-undecylimidazole(1'))ethyl-triazine, 2,4-diamino-6(2'-ethyl-4-methylimidazole(1'))ethyl-triazine, 2,4-diamino-6(2'-methylimidazole(1'))ethyl-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, etc.

[0125] Examples of acid anhydride-based curing agents include: phthalic anhydride, trimellitic anhydride, pyromellitic tetracarboxylic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, biphenyl tetracarboxylic anhydride, and other aromatic carboxylic anhydrides; aliphatic carboxylic anhydrides such as azelaic acid, sebacic acid, and dodecanoic acid; tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, chlorobridged anhydride, and bicycloheptenedioic anhydride, and other alicyclic carboxylic anhydrides.

[0126] Examples of carboxylic acid-based curing agents include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid.

[0127] Based on the total amount of the curing composition, the content of the curing agent can be more than 0.01% by mass, or less than 10%, less than 5% by mass, or less than 1% by mass.

[0128] From the viewpoint of obtaining heat storage materials with superior heat storage capacity, the curable composition may also contain heat storage capsules. A heat storage capsule has a heat storage component and an outer shell containing the heat storage component.

[0129] The heat-storing components in heat-storing capsules can be appropriately selected, for example, components with phase transition temperatures suitable for the target temperature, depending on the intended use. From the viewpoint of achieving heat storage effects within practical ranges, other heat-storing components have, for example, solid-liquid phase transition points (melting points) that exhibit solid-liquid phase transitions from -30 to 120°C.

[0130] Heat-retaining components can be, for example, chain-like (straight-chain or branched) saturated hydrocarbon compounds (paraffinic hydrocarbon compounds), polyalkylene glycols, natural waxes, petroleum waxes, sugar alcohols, etc. From the viewpoint that it is easy to select components that are inexpensive, have low toxicity, and have the desired phase transition temperature, other heat-retaining components are preferably chain-like saturated hydrocarbon compounds (paraffinic hydrocarbon compounds).

[0131] Specifically, the chain-like saturated hydrocarbon compounds can be n-decane (C10, -29℃, transformation point / melting point), n-undecane (C11, -25℃), n-dodecane (C12, -9℃), n-tridecane (C13, -5℃), n-tetradecane (C14, 6℃), n-pentadecanane (C15, 9℃), n-hexadecane (C16, 18℃), n-heptadecane (C17, 21℃), n-octadecane (C18, 28℃), n-nonadecanane (C19, 32℃), n-eicosane (C20, 37℃), n-tetradecane (…). Examples of linear saturated hydrocarbon compounds include: n-dodecane (C21, 41℃), n-toctane (C22, 46℃), n-tridecane (C23, 47℃), n-tetracosane (C24, 50℃), n-pentane (C25, 54℃), n-hexadecane (C26, 56℃), n-heptadecane (C27, 60℃), n-octadecane (C28, 65℃), n-nonadecane (C29, 66℃), n-triacontane (C30, 67℃), n-tetradecane (C40, 81℃), n-pentane (C50, 91℃), n-hexadecane (C60, 98℃), and n-cocacontane (C100, 115℃). Chain-like saturated hydrocarbon compounds can be branched saturated hydrocarbon compounds having the same number of carbon atoms as these linear saturated hydrocarbon compounds. Chain-like saturated hydrocarbon compounds can be one or more of these.

[0132] The shell containing these heat-retaining components is preferably made of a material having a heat resistance temperature sufficiently high than the transition point (melting point) of the heat-retaining components. The material forming the shell has a heat resistance temperature of, for example, 30°C or higher, preferably 50°C or higher, relative to the transition point (melting point) of the heat-retaining components. Furthermore, the heat resistance temperature is defined as the temperature at which the weight of the capsule decreases by 1% when measured using a differential calorimetry-thermogravimetric assay device (e.g., TG-DTA6300 (manufactured by Hitachi High-Tech Science Corporation)).

[0133] As the material forming the outer shell, a material with strength corresponding to the application of the heat storage material formed from the curable composition is appropriately selected. The outer shell can preferably be formed from melamine resin, acrylic resin, polyurethane resin, silica, etc. Examples of microcapsules having an outer shell containing melamine resin include, for example, BA410xxP, 6C, BA410xxP, 18C, BA410xxP, 37C manufactured by Outlast Technologies, Inc.; Thermo-Memory FP-16, FP-25, FP-31, FP-39 manufactured by Mitsubishi Paper Mills Limited; and RIKEN RESIN PMCD-15SP, 25SP, 32SP manufactured by MIKIRIKEN INDUSTRIAL CO., LTD. Examples of microcapsules having an outer shell containing acrylic resin (polymethyl methacrylate resin) include Micronal DS5001X, 5040X manufactured by BASF. Examples of microcapsules having a shell containing silica include RIKEN RESIN LA-15, LA-25, and LA-32 manufactured by MIKIRIKEN INDUSTRIAL CO.,LTD.

[0134] From the viewpoint of further improving the heat storage effect, based on the total amount of heat storage capsules, the content of heat storage components in the heat storage capsules is preferably 20% by mass or more, more preferably 60% by mass or more, and from the viewpoint of suppressing capsule breakage caused by volume changes of heat storage components, it is preferably 80% by mass or less.

[0135] To adjust the thermal conductivity, specific gravity, and other properties of the capsule, heat-retaining capsules may also contain graphite, metal powder, alcohol, etc., inside the outer shell.

[0136] The particle size (average particle size) of the heat-retaining capsules is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.5 μm or more, preferably 100 μm or less, and more preferably 50 μm or less. The particle size (average particle size) of the heat-retaining capsules is determined using a laser diffraction particle size distribution measuring device (e.g., SALD-2300 (manufactured by Shimadzu Corporation)).

[0137] From the viewpoint of further improving the heat storage effect, the content of the heat storage capsule, based on the total amount of the curable composition, is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. From the viewpoint of inhibiting the heat storage capsule from falling off the cured product of the curable composition, the content of the heat storage capsule, based on the total amount of the curable composition, is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0138] From the viewpoint of improving the thermal reliability of the cured product (heat storage material) of the curable composition, the curable composition may also contain antioxidants. Antioxidants may include, for example, phenolic antioxidants, benzophenone antioxidants, benzoate antioxidants, hindered amine antioxidants, benzotriazole antioxidants, etc.

[0139] Based on the total amount of the curable composition, the content of antioxidant can be 0.1% by mass or more, 0.5% by mass or more, 0.8% by mass or more, or 1% by mass or more, or 10% by mass or less or 5% by mass or less. From the viewpoint of excellent softness of the cured product of the curable composition, it is preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2.5% by mass or less, and especially preferably 2% by mass or less.

[0140] The curable composition may also contain other additives as needed. Examples of other additives include, for instance, surface treatment agents, curing accelerators, colorants, fillers, nucleating agents, heat stabilizers, thermally conductive materials, plasticizers, foaming agents, flame retardants, vibration damping agents, dehydrating agents, and flame retardant auxiliaries (e.g., metal oxides). Other additives may be used alone or in combination of two or more. Based on the total amount of the curable composition, the content of other additives may be, for example, 0.1% by mass or more, or 30% by mass or less.

[0141] The curable composition can be in a liquid state at 50°C. Therefore, even between parts with complex shapes, the curable composition can be easily placed by methods such as filling. In this case, from the viewpoint of excellent flowability and processability, the viscosity of the curable composition at 50°C is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, even more preferably 20 Pa·s or less, particularly preferably 10 Pa·s or less, for example, it can be 0.5 Pa·s or more. The viscosity of the curable composition refers to the value measured according to JIS Z8803, specifically, the value measured by an E-type viscometer (e.g., manufactured by TOKI SANGYO CO., LTD., PE-80L). Furthermore, the viscometer can be calibrated according to JIS Z8809-JS14000.

[0142] The curable composition described above, by combining a compound having two (meth)acryloyl groups represented by formula (1) with a compound formed by etherifying the terminal hydroxyl groups of at least one of the polyalkylene glycols, can form a heat storage material with excellent reliability under high temperature and high humidity conditions. The reason for this is that, during curing of the curable composition, by etherifying the terminal hydroxyl groups, the polyalkylene glycol ether, which improves reliability under high temperature and high humidity conditions, can be well incorporated into the crosslinked structure formed from the compound represented by formula (1), thus improving resistance to external moisture through these synergistic effects. Furthermore, the cured product of the curable composition exhibits excellent heat storage capacity due to the compound represented by formula (1) and the polyoxyalkylene chain in the polyalkylene glycol ether. Therefore, this curable composition is preferably used as a curable composition for forming a heat storage material, and the cured product of the curable composition can preferably be used as a heat storage material.

[0143] [Heat storage materials]

[0144] One embodiment of the heat storage material includes a cured product of the above-described curable composition. Figure 1 This is a schematic cross-sectional view illustrating one embodiment of the heat storage material. (Example) Figure 1 As shown in (a), the heat storage material 1A according to one embodiment is a sheet-like (or film-like) heat storage material having a heat storage layer 2 as a cured product of the above-mentioned curable composition.

[0145] like Figure 1 As shown in (b), in another embodiment, the heat storage material 1B is a sheet-like (or film-like) heat storage material comprising a heat storage layer 2 as a cured product of the aforementioned curable composition and an adhesive layer 3 disposed on one side of the heat storage layer 2. In this case, the heat storage material 1B can be suitably bonded to the object to which the heat storage material 1B is applied.

[0146] In each of the embodiments, the thickness of the heat storage layer 2 can be, for example, 0.01 mm or more, 0.05 mm or more, 0.1 mm or more, or 0.2 mm or more, or less than 20 mm, less than 10 mm, or less than 5 mm.

[0147] In each of the embodiments, the heat storage layer 2 can be a cured product formed by fully curing the curing composition, or a cured product formed by B-stage curing (semi-curing) of the curing composition. Figure 1 In the heat storage material 1A shown in (a), from the viewpoint that the heat storage material 1A can be appropriately bonded to the object to which the heat storage material 1A is applied, the heat storage layer 2 is preferably a cured product formed by B-stage curing (semi-curing) of the curable composition.

[0148] The adhesive layer 3 may contain a known adhesive. The thickness of the adhesive layer 3 may be, for example, 0.001 mm or more, 0.003 mm or more, or 0.005 mm or more, or less than 0.03 mm, less than 0.02 mm, or less than 0.015 mm.

[0149] Heat storage material 1A and heat storage material 1B (collectively referred to as heat storage material 1) can be flexibly applied to various fields. For example, heat storage material 1 can be used in air conditioning equipment in automobiles, buildings, public facilities, underground streets, etc. (to improve the efficiency of air conditioning equipment), piping in factories, etc. (heat storage of piping), automobile engines (heat insulation around the engine), electronic components (to prevent electronic components from overheating), and underwear fibers, etc.

[0150] The heat storage layer 2 in the aforementioned heat storage material 1A or the heat storage layer 2 and adhesive layer 3 in the aforementioned heat storage layer 1B can be disposed on the support film. That is, the heat storage material according to another embodiment can include a support film and a heat storage layer 2 disposed on the support film. The heat storage material according to yet another embodiment can include a support film, a heat storage layer 2 disposed on the support film, and an adhesive layer 3 disposed on the side of the heat storage layer 2 opposite to the support film. The heat storage materials according to these embodiments can, for example, be formed in the form of a strip and wound along its long side on a core (roller-shaped heat storage material).

[0151] The support membrane can be formed from polymers such as polyethylene terephthalate, polyethylene, polyvinylidene chloride, polyester, polypropylene, polyvinyl chloride, polycarbonate, polyacrylonitrile, polyetheretherketone, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyimide, and polyamide-imide.

[0152] The thickness of the support film can be, for example, 10 μm or more, 30 μm or more, or 50 μm or more, or less than 200 μm, 150 μm or less, 100 μm or less, 70 μm or less.

[0153] [Items and their manufacturing methods]

[0154] Next, regarding articles containing heat storage material 1 (cured form of a curable composition) and methods for manufacturing thereof, electronic components that are objects to which the heat storage material 1 is disposed will be described.

[0155] Figure 2 This is a schematic cross-sectional view illustrating one embodiment of an article and its manufacturing method. In one embodiment of the article manufacturing method, firstly, as... Figure 2 As shown in (a), an electronic component 11A is prepared as an object, i.e., an article, for which a heat storage material is disposed. The electronic component 11A includes, for example, a substrate 12 and a semiconductor chip (heat source) 13 disposed on the substrate 12.

[0156] Next, as Figure 2 As shown in (b), the heat storage material 1 is configured to be in thermal contact with the substrate 12 and the semiconductor chip 13, respectively. The heat storage material 1 can be, for example, the one described above. Figure 1 The heat storage material 1A shown in (a) can also be the one described above. Figure 1 (b) shows the heat storage material 1B. In use... Figure 1 In the case of the heat storage material 1B shown in (b), the heat storage material 1B is disposed in such a way that the adhesive layer 3 contacts the substrate 12 and the semiconductor wafer 13.

[0157] When the heat storage layer in the heat storage material 1 is a cured product formed by B-stage curing (semi-curing) of a curable composition, the heat storage layer is cured after the heat storage material 1 is disposed. That is, the manufacturing method of the article in this embodiment may further include a step of curing the heat storage layer of the heat storage material 1 disposed on the substrate 12 and the semiconductor wafer 13.

[0158] Thus, an article 14A comprising a substrate 12, a semiconductor wafer 13, and a heat storage material 1 (a cured product of a curable composition) disposed on the substrate 12 and the semiconductor wafer 13 can be obtained.

[0159] In the above embodiment, the heat storage material 1 is configured to cover the entire exposed surface of the heat source 13. However, in another embodiment, the heat storage material may be configured to cover only a portion of the exposed surface of the heat source.

[0160] Figure 3 (a) is a schematic cross-sectional view showing another embodiment of the article. For example... Figure 3 As shown in (a), in another embodiment of article 14B, the heat storage material 1 can be configured to contact (in a way of covering) a portion of the exposed surface of the semiconductor wafer (heat source) 13. The location where the heat storage material 1 is configured (the location where the heat storage material 1 contacts the semiconductor chip 13) is... Figure 3 (a) shows the side portion of the semiconductor chip 13, but it can be on any surface of the semiconductor chip 13.

[0161] Figure 3 (b) is a schematic cross-sectional view showing another embodiment of the article. Figure 3(b) In another embodiment of article 14C, the heat storage material 1 is disposed on the side of the substrate 12 opposite to the side where the semiconductor chip 13 is disposed. In this embodiment, the heat storage material 1 does not directly contact the semiconductor chip 13, but is in thermal contact with the semiconductor chip 13 via the substrate 12. Regarding the location of the heat storage material 1, it can be disposed on any surface of the substrate 12 as long as it is in thermal contact with the semiconductor chip 13. Even in this case, the heat generated by the heat source (semiconductor chip) 13 is effectively conducted to the heat storage material 1 via the substrate 12 and suitably stored in the heat storage material 1.

[0162] In the manufacturing method described in the above embodiment, the heat storage material 1 is in sheet form. However, in another manufacturing method, a liquid curable composition can also be used to manufacture the article (forming the heat storage material).

[0163] Figure 4 This is a schematic cross-sectional view illustrating another embodiment of a method for manufacturing an article. In the forming method (manufacturing method) according to this embodiment, firstly, as... Figure 4 As shown in (a), an electronic component 11B is prepared as an object, i.e., an article, for which a heat storage material is disposed. The electronic component 11B includes, for example, a substrate (e.g., a circuit board) 12, a semiconductor chip (heat source) 13 disposed on the substrate 12, and a plurality of connection portions (e.g., solder) 15 connecting the semiconductor chip 13 to the substrate 12. The plurality of connection portions 15 are separated from each other and disposed between the substrate 12 and the semiconductor chip 13. That is, there is a gap between the substrate 12 and the semiconductor chip 13 that separates the plurality of connection portions 15 from each other.

[0164] Next, as Figure 4 As shown in (b), a curable composition 21 is filled between the substrate 12 and the semiconductor chip 13 using, for example, a syringe 16. The curable composition 21 is the curable composition involved in the above embodiments. The curable composition 21 can be in a completely uncured state or in a partially cured state.

[0165] When the curable composition 21 is in a liquid state at room temperature (e.g., 25°C), it can be filled at room temperature. When the curable composition 21 is in a solid state at room temperature, it can be heated (e.g., to 50°C or higher) to form a liquid state before being filled.

[0166] By filling the curable composition 21 in the manner described above, such as Figure 4 As shown in (c), the curable composition 21 is configured to make thermal contact with the substrate 12, the semiconductor chip 13 and the connecting portion 15 in the gap between the substrate 12 and the semiconductor chip 13.

[0167] Next, the curable composition 21 is cured, such as... Figure 4 As shown in (d), a cured product (also called a heat storage layer or heat storage material) 22 of the curable composition is formed in the gap between the substrate 12 and the semiconductor wafer 13. Thus, an article 14D can be obtained, which includes: a substrate 12; a semiconductor wafer (heat source) 13 disposed on the substrate 12; a plurality of connecting portions 15 connecting the semiconductor wafer 13 and the substrate 12; and a cured product (heat storage layer or heat storage material) 22 of the curable composition disposed in such a way as to fill the gap formed by the substrate 12, the semiconductor wafer (heat source) 13 and the plurality of connecting portions 15.

[0168] The curing method of the curable composition 21 can be as follows: if the curable composition 21 contains a polymerization initiator, the curable composition 21 is cured by heating the prepared curable composition 21. The curing method of the curable composition 21 can also be as follows: if the curable composition 21 contains a polymerization initiator, the curable composition 21 is cured by irradiating the curable composition 21 with light (e.g., light containing at least a portion of the wavelengths from 200 to 400 nm (ultraviolet light)). The curing method can be any one or a combination of two or more of these methods.

[0169] In the above embodiments, the heat storage material 1 (cured product 22 of the curable composition) is configured to be in direct contact with the semiconductor chip 13, which is a heat source. However, the heat storage material and the cured product of the curable composition only need to be in thermal contact with the heat source. In another embodiment, for example, they can also be configured to be in thermal contact with the heat source via a thermally conductive component (heat-dissipating component, etc.).

[0170] Example

[0171] The present invention will be described in more detail below through embodiments, but the present invention is not limited to the following embodiments.

[0172] [Synthesis of compound (A-1)]

[0173] A 500 mL flask, consisting of a stirrer, thermometer, nitrogen inlet tube, outlet tube, and heating mantle, was used as a reactor. 15 g of polyethylene glycol #1000 (weight average molecular weight: 1000, manufactured by Sanyo Chemical Industries, Ltd.) and 300.0 g of toluene were added to the reactor. The mixture was stirred at 45°C at a stirring speed of 250 rpm, with nitrogen flowing through at 100 mL / min for 30 minutes. Then, the temperature was lowered to 25°C. After cooling, 2.9 g of acryloyl chloride was added dropwise to the reactor, and the mixture was stirred for 30 minutes. Next, 3.8 g of triethylamine was added dropwise, and the mixture was stirred for 2 hours. The temperature was then raised to 45°C, and the reaction was allowed to proceed for 2 hours. The reaction solution was filtered, and the filtrate was desolvated to obtain compound (A-1) represented by the following formula (1-3) with a weight average molecular weight of 1000.

[0174]

[0175] [Synthesis of compound (A-2)]

[0176] Except that 45g of polyethylene glycol 4,000 (weight average molecular weight: 2700-3300, manufactured by FUJIFILM Wako PureChemical Corporation) was used instead of 15g of polyethylene glycol #1000, compound (A-2) with a weight average molecular weight of 3400, represented by the above formula (1-3), was obtained in the same manner as compound (A-1).

[0177] [Synthesis of compound (A-3)]

[0178] Except that 120g of polyethylene glycol 6,000 (weight average molecular weight: 7300-9300, manufactured by FUJIFILM Wako PureChemical Corporation) was used instead of 15g of polyethylene glycol #1000, compound (A-3) with a weight average molecular weight of 8000 was obtained in the same manner as compound (A-1), as represented by the above formula (1-3).

[0179] In the embodiments, in addition to compounds (A-1) to (A-3) mentioned above, the following components were used.

[0180] (B-1) Polyethylene glycol monomethyl ether (weight average molecular weight: 1000)

[0181] (B-2) Polyethylene glycol dimethyl ether (weight average molecular weight: 1000)

[0182] (B-3) Polyethylene glycol monomethyl ether (weight average molecular weight: 4000)

[0183] (b-1): Polyethylene glycol (weight average molecular weight: 1000)

[0184] (C-1): Methoxylated polyethylene glycol acrylate (weight average molecular weight: 550)

[0185] (C-2): Methoxylated polyethylene glycol acrylate (weight average molecular weight: 1000)

[0186] (D-1) Antioxidant (Adekastab AO-80, manufactured by Adekastab Inc.)

[0187] (D-2) Polymerization initiator (Omnirad 1173, manufactured by IGM Resins BV)

[0188] [Production of thermal storage materials]

[0189] The components were mixed at 70°C according to the mixing ratios shown in Tables 1 and 2 to obtain the curable compositions of the Examples and Reference Examples. Next, at 70°C, using a spacer, the cured composition was coated onto a PET film to a thickness of 200 μm after curing, and then the PET film was wrapped over the coated surface. For this, a metal halide lamp manufactured by Ushio Inc. was used to achieve an illuminance of 130 mW / cm². 2 Cumulative light intensity 4000mJ / cm 2 The above method of irradiating with UV light yields a heat storage material (a cured product of a curable composition).

[0190] Reliability testing under high temperature and high humidity conditions

[0191] Three 30mm × 30mm specimens were cut from each of the heat storage materials (cured products) in the Examples and Reference Examples, and their weights (initial weights) were measured. These specimens were then left to stand for 1 hour at 85°C and 85% RH. The surfaces of the specimens after standing were visually observed, and liquid exudation was confirmed on the surfaces of the specimens in Reference Example 1, Examples 1-2, Examples 4-5, and Example 9. For each specimen where exudation was confirmed, the liquid component on the surface was wiped off with lens paper (manufactured by NIPPON PAPER CRECIA CO.,LTD.), and the weights (post-test weights) of the three types of specimens were measured. The average value of the three types of specimens was calculated based on the weight change rate obtained according to the following formula.

[0192] Weight change rate (%) = (weight after test - initial weight) / initial weight × 100

[0193] In addition, for the remaining samples of the embodiment where no liquid component was detected, the weight (post-test weight) of the three samples was also measured, and the average value of the three samples was calculated based on the weight change rate obtained according to the above formula. The weight change rate calculated as described above is shown in Tables 1 and 2.

[0194] [Determination of heat storage]

[0195] For each heat storage material (cured product) in the embodiments, the heat storage capacity was calculated using a differential scanning calorimeter (TA Instruments Japan Inc., model Discovery DSC250). Specifically, the thermal behavior of each heat storage material was measured by heating to 100°C at a rate of 20°C / min, holding at 100°C for 3 minutes, cooling to -20°C at a rate of 3°C / min, holding at -20°C for 3 minutes, and then heating back to 100°C at a rate of 3°C / min. The area of ​​the melting peak was calculated as the heat storage capacity. The results are shown in Tables 1 and 2.

[0196] [Table 1]

[0197]

[0198] [Table 2]

[0199]

[0200] When the rate of change of weight is negative, it means that the liquid component has seeped out of the sample surface. In this case, the larger the absolute value, the greater the amount of seepage. It is assumed that the liquid component is polyethylene glycol or polyethylene glycol ether. On the other hand, when the rate of change of weight is positive, the liquid component does not seep out of the sample surface. It is assumed that the heat storage material absorbs and encapsulates moisture in a high temperature and high humidity environment. That is, it can be said that the reliability under high temperature and high humidity is better when the rate of change of weight is positive than when it is negative. In addition, when the rate of change of weight is negative, it can be said that the smaller the absolute value, the better the reliability under high temperature and high humidity. According to Tables 1 and 2, the compounds represented by formula (1) and polyalkylene glycol ether in Examples 1 to 13 have better reliability under high temperature and high humidity than the compounds represented by formula (1) and polyalkylene glycol in Reference Example 1.

[0201] Symbol Explanation

[0202] 1, 1A, 1B - heat storage material; 2 - heat storage layer; 3 - adhesive layer; 11A, 11B - electronic components; 12 - substrate; 13 - semiconductor wafer (heat source); 14A, 14B, 14C, 14D - articles; 15 - connector; 16 - syringe; 21 - curable composition; 22 - cured product of curable composition (heat storage material).

Claims

1. A curable composition comprising: The compound represented by the following formula (1); and At least one polyalkylene glycol ether selected from the group consisting of polyalkylene glycol monoethers and polyalkylene glycol diethers. And it contains compounds represented by formula (1) having a weight average molecular weight of 2000 or more as compounds represented by formula (1). In equation (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 13 This indicates a divalent group having a polyoxyalkylene chain.

2. The curable composition according to claim 1, wherein the polyalkylene glycol ether has a weight-average molecular weight of 400 or more is said polyalkylene glycol ether.

3. The curable composition according to claim 1, wherein the polyalkylene glycol ether has a weight-average molecular weight of less than 5000 is the polyalkylene glycol ether.

4. The curable composition according to claim 1, further comprising a compound represented by formula (3) below, In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 This indicates a monovalent group having a polyoxyalkylene chain.

5. The curable composition according to any one of claims 1 to 4, used to form a heat storage material.

6. A heat storage material comprising a cured product of the curable composition according to any one of claims 1 to 5.

7. An item that possesses: Heat source; and A cured product of any one of claims 1 to 5, provided in a manner that allows it to come into thermal contact with the heat source.

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