Hardened components, heat storage materials and articles

Abstract

A curable composition comprising a compound represented by formula (1) below, and at least one polyalkylene glycol ether selected from the group consisting of polyalkylene glycol monoethers and polyalkylene glycol diethers. In formula (1), R11 and R12 independently represent a hydrogen atom or a methyl group, respectively, and R13 represents a divalent group having a polyoxyalkylene chain.

Description

Technical Field

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

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

[0003] In terms of the amount of heat, latent heat storage based on the phase change of the material can be widely utilized as a method of heat storage. For example, Patent Document 1 discloses a heat storage material composition containing polyalkylene glycol as a latent heat storage component. [Existing Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2006-96898 Summary of the Invention

[0005] [The problem that the invention aims to solve]

[0006] According to the research conducted by the present invention, there is room for further improvement in the reliability of heat storage materials containing polyalkylene glycol under high temperature and high humidity environments. Therefore, in one aspect, an object of the present invention is to provide a hardenable composition that can form a heat storage material with excellent reliability under high temperature and high humidity environments. [Methods for solving problems]

[0007] The inventors have conducted diligent research and discovered that by combining a specific compound having a polyoxyalkylene chain and having two (meth)acrylic groups with a compound formed by etherifying at least one terminal hydroxyl group 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 several aspects, the present invention provides the following [1] to [8].

[0008] [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. [Chemistry 1] In formula (1), R11 and R12 independently represent hydrogen atoms or methyl groups, respectively, and R13 represents a divalent group with a polyoxyalkylene chain. [2] The curing composition as described in [1] contains a compound represented by formula (1) having a weight average molecular weight of 1000 or more. [3] The curable composition as described in [1] or [2] contains a polyalkylene glycol ether having a weight average molecular weight of 400 or more as a polyalkylene glycol ether. [4] The curing composition as described in any one of [1] to [3] contains a polyalkylene glycol ether having a weight average molecular weight of less than 5,000 as a polyalkylene glycol ether. [5] The curing composition as described in any one of [1] to [4] further contains a compound represented by the following formula (3). [Chemistry 2] In formula (3), R 31 represents a hydrogen atom or a methyl group, and R 32 represents a monovalent group with a polyoxyalkylene chain. [6] The hardening composition as described in any one of [1] to [5] is used to form a heat storage material. [7] A heat storage material comprising a hardened material containing a hardening composition as described in any one of [1] to [6]. [8] An article comprising: a heat source; and a hardened composition of any one of [1] to [6] disposed in thermal contact with the heat source. [The effects of the invention]

[0009] According to one aspect of the present invention, a hardenable composition capable of forming a heat storage material with excellent reliability under high temperature and high humidity conditions can be provided. Simple Explanation of the Diagram

[0010] Figure 1(a) and Figure 1(b) are schematic cross-sectional views showing one embodiment of the heat storage material. Figure 2(a) and Figure 2(b) are schematic cross-sectional views showing one embodiment of the article and its manufacturing method. Figure 3(a) and Figure 3(b) are schematic cross-sectional views showing another embodiment of the article. Figures 4(a) to 4(d) are schematic cross-sectional views showing another embodiment of the method of manufacturing the article. Implementation

[0011] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments.

[0012] The term "(meth)acrylic" in this specification refers to "acrylic" and its corresponding "methacrylic," and the same applies to similar expressions such as "(meth)acrylate" and "(meth)acrylic acid."

[0013] The weight-average molecular weight (Mw) in this specification refers to the value determined using gel permeation chromatography (GPC) under the following conditions, with polystyrene as the standard substance. • Measuring machine: HLC-8320GPC (Product name, manufactured by Tosoh Corporation) • Analytical column: TSKgel SuperMultipore HZ-H (3-connector) (Product name, manufactured by Tosoh Corporation) • Guard column: TSKguardcolumn SuperMP(HZ)-H (Product name, manufactured by Tosoh Corporation) • Dissolution solution: Tetrahydrofuran (THF) • Measurement temperature: 25℃

[0014] [Hardening composition] 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. [Chemistry 3] In formula (1), R11 and R12 independently represent hydrogen atoms or methyl groups, respectively, and R13 represents a divalent group with a polyoxyalkylene chain.

[0015] In one embodiment, one of R11 and R12 may be a hydrogen atom and the other may be a methyl group; in another embodiment, both R11 and R12 may be hydrogen atoms; and in yet another embodiment, both R11 and R12 may be methyl groups.

[0016] Polyoxyalkyl chains are represented, for example, by the following formula (1-1). [Chemistry 4] In formula (1-1), R 14 represents an alkyl group, m represents an integer greater than 2, and * represents a bond.

[0017] The alkyl group represented by R 14 can be linear or branched. R 14 can be, for example, an alkyl group having 2 to 4 carbon atoms. Multiple R 14s in the polyoxyalkylene chain can be identical or different from each other. Preferably, the multiple R 14s in the polyoxyalkylene chain are selected from one or more of the group consisting of ethyl, propyl, and butyl groups; more preferably, they are selected from one or two of the group consisting of ethyl and propyl groups; and most preferably, all of them are ethyl groups.

[0018] m can be an integer of 10 or more or 20 or more, and can be an integer of 300 or less, 250 or less or 200 or less. From the viewpoint that a heat storage material with better reliability under high temperature and high humidity conditions can be obtained by making m an integer of 1000 or more of the molecular weight of the compound represented by formula (1), 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 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.

[0019] R 13 can also be a divalent group that has other organic groups besides polyoxyalkylene chains. Other organic groups can be chain-like groups other than polyoxyalkylene chains, such as methylene chains (chains with -CH 2- as structural units), polyester chains (chains containing -COO- in structural units), polyurethane chains (chains containing -OCON- in structural units), etc.

[0020] The compound represented by formula (1) is preferably the compound represented by formula (1-2) below. [Chemistry 5] In equation (1-2), R11 and R12 have the same meaning as R11 and R12 in equation (1), and R14 and m have the same meaning as R14 and m in equation (1-1).

[0021] From the viewpoint that a heat storage material with superior reliability under high temperature and high humidity conditions can be obtained by having a weight average molecular weight (Mw) of the compound represented by formula (1) of, for example, 1000 or more, it is preferable to have a weight average molecular weight (Mw) 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 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.

[0022] The curing composition may contain one compound represented by formula (1) having the stated 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 method described above, 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.

[0023] From the viewpoint that a heat storage material with superior heat storage can be obtained in one embodiment, the hardening component preferably contains at least one compound having a Mw of 2000 or more (referred to as compound (1A)), or may 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 preferably 3000 or more, 4000 or more, 5000 or more, 6000 or more, or 7000 or more, for example, it may be 12000 or less, 11000 or less, or 10000 or less. The Mw of compound (1B) may be, for example, 1000 or more, and may be 1500 or less.

[0024] Based on the total amount of the curing 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 curing 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. Furthermore, if the cured product of the curing composition has excellent flexibility, it can be used by bending, for example, so the cured product is more suitable for use as a heat storage material that can be applied to a wider range of applications. Based on the total amount of the curing 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 curing composition contains two or more compounds represented by formula (1), their total amount can be within the range described above. When the curing composition contains the compound (1A) and / or the compound (1B), the total amount of the compound (1A) and the compound (1B) may be within the range, and the content of each of the compound (1A) and the compound (1B) may be within the range.

[0025] In the case where the curing composition contains compounds that can copolymerize with the compound represented by formula (1) in addition to 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 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") of 100 parts by mass. From the viewpoint that the curing composition has excellent flexibility and can obtain a heat storage material with better heat storage, it is more preferably 10 parts by mass or more or 15 parts by mass, 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, and even more preferably 40 parts by mass or more. The content of the compound represented by formula (1) may 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 content of the polymerizable components of 100 parts by mass.

[0026] Polyalkyl glycol ethers are represented, for example, by the following formula (2). [Chemistry 6] In formula (2), R21 and R22 independently represent a hydrogen atom or a monovalent hydrocarbon group, R23 represents an alkyl group, and n represents an integer greater than 2. At least one of R21 and R22 represents a monovalent hydrocarbon group. When only one of R21 and R22 is a monovalent hydrocarbon group, the polyalkylene glycol ether is a polyalkylene glycol monoether. When both R21 and R22 are monovalent hydrocarbon groups, the polyalkylene glycol ether is a polyalkylene glycol diether.

[0027] The monovalent hydrocarbon group represented by R 21 and R 22 can be, for example, alkyl or aryl, preferably alkyl. The alkyl group can be straight-chain or branched. The alkyl group can have, for example, 1 or more carbon atoms, 10 or less, 8 or less, 6 or less, 4 or less, or 2 or less. As an aryl group, phenyl can be listed as an example.

[0028] The alkyl group represented by R 23 can be linear or branched. From the viewpoint of obtaining a heat storage material with superior heat storage capacity, a linear form is preferred. R 23 can be, for example, an alkyl group having 2 to 4 carbon atoms. Multiple R 23s in a molecule can be the same or different from each other. It is preferable that all R 23s in a molecule are alkyl ethyl groups.

[0029] In one embodiment, it is preferred that the monovalent hydrocarbon groups represented by R 21 and R 22 are alkyl groups and that all the alkyl groups represented by R 23 are ethyl groups. That is, the polyalkylene glycol ether is preferably selected from at least one group consisting of polyethylene glycol monoalkyl ethers and polyethylene glycol dialkyl ethers.

[0030] n can be an integer of 10 or more or 20 or less, 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 that the reliability improvement effect under high temperature and high humidity environment is further increased by etherifying the terminal hydroxyl groups of polyalkylene glycol, n is preferably an integer whose molecular weight is 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0031] The weight-average molecular weight (Mw) of the compound represented by formula (2) may 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 that the reliability improvement effect under high temperature and high humidity environment is further enhanced by etherifying the terminal hydroxyl groups of 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.

[0032] From the viewpoint that a heat storage material with superior heat storage can be obtained by having a polyalkylene glycol ether content of, for example, 10% by mass or more based on the total amount of curable components, it is preferable to have a content of 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 curable components, the polyalkylene glycol ether content 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.

[0033] From the viewpoint that a heat storage material with superior heat storage can be obtained by having a polyalkylene glycol ether content of 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more relative to the total content of polymeric components, 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, and it can 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. Relative to the total content of polymeric components, the polyalkylene glycol content 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.

[0034] The curing composition may further contain a polymerization initiator. There are no particular limitations on whether the polymerization initiator is a compound that can initiate the polymerization of the compound represented by formula (1) and, if necessary, a compound that can copolymerize with the compound represented by formula (1) (details will be 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.

[0035] When the curing composition contains a thermal polymerization initiator, a cured product of the curing composition can be obtained by applying heat to the curing composition. In this case, the curing composition can be a curing composition that is cured by heating at a temperature preferably above 105°C, more preferably above 110°C, and even more preferably above 115°C, and can be a curing composition that is cured by heating at, for example, below 200°C, below 190°C, or below 180°C. The heating time when heating the curing composition can be appropriately selected according to the composition of the curing composition to ensure that the curing composition is properly cured.

[0036] Examples of thermal polymerization initiators include: azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylpentanonitrile, azobiscyclohexanone-1-carboxynitrile, azobisbenzoxylene, and other azo compounds; and organic peroxides such as benzoyl peroxide, lauryl peroxide, di-tert-butylperoxyhexahydrophthalic acid ester, tert-butylperoxy-2-ethylhexanoate, 1,1-tert-butylperoxy-3,3,5-trimethylcyclohexane, and tert-butylperoxyisopropyl carbonate. One or more of these can be used alone or in combination as thermal polymerization initiators.

[0037] When the curing composition contains a photopolymerization initiator, a cured product of the curing composition can be obtained, for example, by irradiating the curing 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 photopolymerization initiator.

[0038] 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, benzophenone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanone-based photopolymerization initiators, and acetylated phosphine oxide-based photopolymerization initiators, etc.

[0039] 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), anisole methyl ether, etc. Examples of acetophenone-based photopolymerization initiators include: 1-hydroxycyclohexylphenyl ketone (manufactured under trade names: Omnirad 184, IGM Resins BV), 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (manufactured under trade names: Omnirad 2959, IGM Resins BV), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (manufactured under trade names: Omnirad 1173, IGM Resins BV), and methoxyacetophenone.

[0040] 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.

[0041] Examples of benzoin-based photopolymerization initiators include benzoin. Examples of benzoin-based photopolymerization initiators include benzoin. Examples of benzophenone-based photopolymerization initiators include benzophenone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, and α-hydroxycyclohexylphenyl ketone. Examples of benzyl dimethyl ketal-based photopolymerization initiators include benzyl dimethyl ketal. 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.

[0042] Examples of phosphine oxide photopolymerization initiators include: bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropane-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylpropane-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-tert-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, and bis(2-methoxybenzoyl)cyclohexylphosphine oxide. Phosphorus(2-methylpropane-1-yl)oxide, bis(2-methoxybenzoyl)(1-methylpropane-1-yl)oxide, bis(2,6-diethoxybenzoyl)(2-methylpropane-1-yl)oxide, bis(2,6-diethoxybenzoyl)(1-methylpropane-1-yl)oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropane-1-yl)oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropane-1-yl)oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxyphenyl)oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide ... Benzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2, 4,6-Trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tris(2-methylbenzoyl)phosphine oxide, etc.

[0043] The photopolymerization initiator can be used alone or in combination of two or more.

[0044] From the viewpoint of enabling polymerization to proceed suitably, 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 polymeric components (100 parts by mass). From the viewpoint of ensuring that the molecular weight of the polymer in the cured product of the curable component is within a suitable range, suppressing decomposition products, and obtaining suitable adhesion 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 total content of the polymeric components (100 parts by mass).

[0045] The curing composition may further contain a compound that can copolymerize with the compound represented by formula (1). This copolymerizable compound may, for example, have a group containing an ethylene unsaturated bond (ethylene unsaturated group). Examples of ethylene unsaturated groups include (meth)acryl, vinyl, allyl, etc. Preferably, the copolymerizable compound is a compound containing a (meth)acryl group.

[0046] From the viewpoint of obtaining a heat storage material with superior heat storage capacity, the curable component is preferably a compound represented by the following formula (3) as the copolymerizable compound. [Chemistry 7] In formula (3), R 31 represents a hydrogen atom or a methyl group, and R 32 represents a monovalent group with a polyoxyalkylene chain.

[0047] R 32 can be, for example, a basis represented by the following equation (3-1). [Chemistry 8] In formula (3-1), R 33 represents an alkyl group, R 34 represents a hydrogen atom or an alkyl group, p represents an integer greater than 2, and * represents a bond.

[0048] The alkyl group represented by R 33 can be linear or branched. From the viewpoint of obtaining a heat storage material with superior heat storage capacity, a linear form is preferred. R 33 can be, for example, an alkyl group having 2 to 4 carbon atoms. Multiple R 33s present in the polyoxyalkylene chain can be identical or different from each other. The polyoxyalkylene chain preferably has one or more of the group consisting of oxyethyl, oxypropyl, and oxybutyl, more preferably has one or two of the group consisting of oxyethyl and oxypropyl, and even more preferably has only oxyethyl.

[0049] The alkyl group represented by R 34 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. R 34 is particularly preferably a hydrogen atom or a methyl group.

[0050] 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 of 800 or more, 900 or more, or 1000 or more for the molecular weight of the compound represented by formula (3), and more preferably an integer of 1200 or more, 1400 or more, 1600 or more, 1800 or more, or 2000 or more for the molecular weight of the compound represented by formula (3). p can also be an integer of 5000 or less, 4000 or less, 3000 or less, or 2500 or less for the molecular weight of the compound represented by formula (3).

[0051] 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 be 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0052] From the viewpoint that a heat storage material with superior heat storage can be obtained by having a content of 10 parts by mass or more, 20 parts by mass or more, or 30 parts by mass or more relative to the total content of polymeric components of 100 parts by mass, it is preferable to have a content of 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 relative to the total content of polymeric components of 100 parts by mass, 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.

[0053] From the viewpoint that the cured product of the curing composition can be suitably used as a heat storage material when the curing composition contains the compound represented by formula (3), 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.

[0054] The melting points of the compounds represented by formula (3) and the polyalkylene glycol ethers were determined as follows. A differential scanning calorimeter (e.g., a Discovery Differential Scanning Calorimeter (DSC) 250 manufactured by TA Instruments) was used to raise the temperature to 100°C at a rate of 20°C / min, hold it at 100°C for 3 minutes, then lower the temperature to -20°C at a rate of 3°C / min, hold it at -20°C for 3 minutes, and then raise the temperature back to 100°C at a rate of 3°C / min.

[0055] From the perspective of adjusting the hardness of the hardened component and the view that the polymerization initiator is easy to dissolve in the hardened component when it is solid, the hardened component may further contain the compound represented by the following formula (4) as a compound that can be copolymerized with the compound represented by formula (1). [Chemistry 9] In formula (4), R 41 represents a hydrogen atom or a methyl group, and R 42 represents an alkyl group.

[0056] The alkyl group represented by R 42 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 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0057] The content of the compound represented by formula (4) may be, for example, more than 0.5 parts by mass, more than 1 part by mass, or more than 1.5 parts by mass, and may be 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 polymerizable components.

[0058] The curing composition may further contain the compound represented by formula (5) as a compound that can be copolymerized with the compound represented by formula (1). [Chemistry 10] In formula (5), R 51 represents a hydrogen atom or a methyl group, and R 52 represents a monovalent group with a reactive group.

[0059] In the case where the curing composition further contains the compound represented by formula (5), after polymerizing 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), the reactive group contained in the compound represented by formula (5) reacts with the curing agent described later, thereby further curing the curing composition.

[0060] The reactive group represented by R 52 is a group that can react with the curing agent described later, for example, 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.

[0061] 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.

[0062] 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)acrylate and other hydroxyalkylcycloalkane (meth)acrylate esters. Other hydroxyl-containing compounds include hydroxyethyl (meth)acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.

[0063] Examples of compounds containing isocyanate groups include 2-methacryloxyethyl isocyanate and 2-acryloxyethyl isocyanate.

[0064] The isocyanate groups in compounds containing isocyanate groups can also be blocked (protected) by a blocking agent (protecting group) that can be removed by heat. That is, compounds containing isocyanate groups can also be compounds with blocked isocyanate groups as represented by the following formula (5-1). [Chemistry 11] In the formula, B represents the protecting group, and * represents the bond.

[0065] The protecting group in the blocked isocyanate group can also be a protecting group that can be deprotected by heating (e.g., heating to 80°C~160°C). In the blocked isocyanate group, under deprotection conditions (e.g., heating to 80°C~160°C), a substitution reaction may occur between the blocking agent (protecting group) and the curing agent described later. Alternatively, in the blocked isocyanate group, an isocyanate group is generated by deprotection, and the isocyanate group can also react with the curing agent described later.

[0066] Examples of blocking agents for 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-valerolactamase, γ-butyrolactam, and β-propiolactamase; thiols such as thiophenol, methyl thiophenol, and ethyl thiophenol; acid acetylamine compounds such as acetylamine and benzoylamine; and aceimine compounds such as succinate aceimine and maleate aceimine.

[0067] Examples of compounds having a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and 2-(O-[1'-methylpropylamino]carboxylamino)methacrylate.

[0068] Examples of compounds containing an amino group include: N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, and N,N-diethylaminopropyl methacrylate.

[0069] 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, 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 (meth)acrylate.

[0070] The content of the compound represented by formula (5) may be, for example, more than 0.5 parts by mass, more than 1 part by mass, or more than 1.5 parts by mass, and may be 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 polymerizable components.

[0071] Based on the total amount of curing components, 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, 90% or less by mass, 80% or less by mass, 70% or less by mass, 60% or less by mass, or 50% or less by mass.

[0072] The compound represented by formula (1) and the compound that can be copolymerized with the compound represented by formula (1) may be selected in such a way that the crosslinking density index calculated according to formula (A) below is within the range described below. Crosslinking density index = M / C × 1000 …(A) In the formula, M represents the total number of moles of polymerizable groups (ethylene unsaturated groups) in the polymerizable component (unit: mole), and C represents the total content of the polymerizable component (unit: g).

[0073] From the viewpoint that a crosslinking density index of 2.5 or less can yield a heat storage material with superior 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. A crosslinking density index of 0.1 or more, 0.2 or more, or 0.3 or more is also acceptable.

[0074] When the curing composition contains a compound represented by formula (5), the curing composition preferably further contains a curing agent. The curing agent is a compound that can react with the reactive group contained in the compound represented by formula (5).

[0075] Examples of curing agents include isocyanate-based curing agents, phenolic 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 appropriately selected, either alone or in combination of two or more, depending on the type of reactive group contained in the compound represented by formula (5). For example, when the reactive group is an epoxy group, a phenolic curing agent or an imidazole curing agent is preferred.

[0076] Examples of isocyanate-based curing agents include: toluene diisocyanate (2,4-toluene diisocyanate or 2,6-toluene diisocyanate or mixtures thereof) (TDI), phenyl diisocyanate (m-phenyl diisocyanate or p-phenyl diisocyanate or mixtures thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), and 4,4'-toluidine diisocyanate (…). Aromatic diisocyanates include diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, etc.

[0077] Examples of isocyanate-based curing agents include: trimethylene diisocyanate, 1,2-epimethylene diisocyanate, butyl diisocyanate (tetramethylene diisocyanate, 1,2-epimethylene diisocyanate, 2,3-epimethylene diisocyanate, 1,3-epimethylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), and 1,6-hexamethylene diisocyanate. Diisocyanate (HDI), 2,4,4-trimethylhexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diisocyanate, methyl hexanoate 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-trimethylcyclohexyl isocyanate (isophorone diisocyanate) 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)), trans, trans, trans, 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) (norbornane diisocyanate (NBDI), bis(isocyanomethyl)cyclohexane (1,3-bis(isocyanomethyl)cyclohexane or 1,4-bis(isocyanomethyl)cyclohexane or mixtures thereof) (H6XDI), and other alicyclic diisocyanates.

[0078] 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 terephthalic acid. Phenols, 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 xylylene skeleton; phenolic varnish resins containing a dicyclopentadiene skeleton; phenolic varnish resins containing a biphenyl skeleton; phenolic varnish resins containing a fluorene skeleton; phenolic varnish resins containing a furan skeleton, and other phenolic varnish resins, etc.

[0079] Examples of amine-based curing agents include: aromatic amines such as diaminodiphenylmethane, 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 dicyandiamine and 1-(o-tolyl)biguanide.

[0080] 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.

[0081] Examples of acid anhydride-based curing agents include: phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, 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; and alicyclic carboxylic anhydrides such as tetrahydrophthalic anhydride, hexahydrophthalic anhydride, terephthalic anhydride, chlorobridged anhydride, and bicycloheptenedioic anhydride.

[0082] Examples of carboxylic acid-based curing agents include: succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid.

[0083] Based on the total amount of hardening components, the content of hardener can be 0.01% by mass or more, and can be less than 10% by mass, less than 5% by mass, or less than 1% by mass.

[0084] From the perspective of obtaining heat storage materials with superior heat storage capacity, the hardened composition may further contain heat storage capsules. A heat storage capsule has a heat storage component and an outer shell (shell) containing the heat storage component.

[0085] The heat-storing components in a heat-storing capsule can be appropriately selected, for example, to have a phase transition temperature suitable for the target temperature, depending on the intended use. From the viewpoint of achieving heat storage effect within a practical range, other heat-storing components may have a solid-liquid phase transition point (melting point) that exhibits solid-liquid phase transition within the range of -30°C to 120°C.

[0086] The heat-storing component can be, for example, a chain-like (straight-chain or branched) saturated hydrocarbon compound (paraffinic hydrocarbon compound), polyalkylene glycol, natural wax, petroleum wax, sugar alcohol, etc. From the viewpoint that it is easy to select one that is inexpensive, has low toxicity, and has the desired phase transition temperature, other heat-storing components are preferably chain-like saturated hydrocarbon compounds (paraffinic hydrocarbon compounds).

[0087] Specifically, chain-like saturated hydrocarbon compounds can also be n-decane (C10, -29℃ transfer 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-timodecane (C10, -29℃), n-undecanane (C10, -25℃), n-dodecane (C11, -25℃), n-tetane (C12, -9℃), n-tetane (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 (C10, -25℃), n-tet ... Examples of saturated hydrocarbon compounds include n-dodecane (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 also be branched saturated hydrocarbon compounds having the same number of carbons as these straight-chain saturated hydrocarbon compounds. Chain-like saturated hydrocarbon compounds can also be one or more of these compounds.

[0088] The outer shell (shell) containing the heat-retaining component is preferably made of a material having a heat resistance temperature sufficiently higher than the melting point (transfer point) of the heat-retaining component. The material forming the shell has a heat resistance temperature, for example, 30°C or higher, and preferably 50°C or higher, relative to the melting point (transfer point) of the heat-retaining component. 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 thermal gravimetric assay device (e.g., TG-DTA6300 (manufactured by Hitachi High-Tech Science, Ltd.)).

[0089] 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 can be appropriately selected. The outer shell is preferably formed from melamine resin, acrylic resin, urethane resin, silicon dioxide, etc. Examples of microcapsules having an outer shell containing melamine resin include: BA410xxP,6C, BA410xxP,18C, and BA410xxP,37C manufactured by Outlast Technology; Thermo Memory FP-16, FP-25, FP-31, and FP-39 manufactured by Mitsubishi Paper Industries, Ltd.; and Riken Resin PMCD-15SP, 25SP, and 32SP manufactured by Riken Industries, Ltd. Examples of microcapsules having an outer shell containing acrylic resin (polymethyl methacrylate resin) include Micronal DS5001X and 5040X manufactured by BASF. Examples of microcapsules having a shell containing silicon dioxide include Riken resins LA-15, LA-25, and LA-32 manufactured by Riken Industries, Ltd.

[0090] From the perspective 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 perspective of suppressing capsule breakage caused by volume changes of heat storage components, it is preferably 80% by mass or less.

[0091] For the purpose of adjusting the thermal conductivity and specific gravity of the capsule, heat-storing capsules may also contain graphite, metal powder, alcohol, etc. inside the shell.

[0092] The particle size (average particle size) of the heat-retaining capsule 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 capsule is measured using a laser diffraction particle size distribution measuring device (e.g., SALD-2300 (manufactured by Shimadzu Corporation)).

[0093] From the viewpoint of further improving the heat storage effect, the content of heat storage capsules, based on the total amount of curing components, 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 detachment of heat storage capsules from the curing material of curing components, the content of heat storage capsules, based on the total amount of curing components, is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0094] From the perspective of improving the thermal reliability of the hardened material (heat storage material) with a hardening composition, the hardening composition may further contain antioxidants. Antioxidants may be, for example, phenolic antioxidants, benzophenone antioxidants, benzoate antioxidants, hindered amine antioxidants, benzotriazole antioxidants, etc.

[0095] Based on the total amount of the curing component, the content of antioxidant may 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, and may be 10% by mass or less or 5% by mass or less. From the viewpoint of excellent flexibility of the cured product of the curing component, it is preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2.5% by mass or less, and especially preferably 2% by mass or less.

[0096] The curing composition may contain other additives as needed. Examples of such additives include: surface treatment agents, curing accelerators, colorants, fillers, nucleating agents, heat stabilizers, heat conductors, plasticizers, foaming agents, flame retardants, vibration dampers, 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 curing composition, the content of other additives may be 0.1% by mass or more, and may be less than 30% by mass.

[0097] The curing composition is liquid at 50°C. Therefore, it can be easily applied to components with complex shapes by filling or other methods. In this case, from the viewpoint of excellent flowability and operability, the viscosity of the curing composition at 50°C is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, further preferably 20 Pa·s or less, particularly preferably 10 Pa·s or less, and for example, 0.5 Pa·s or more. The viscosity of the curing composition refers to a value measured according to Japanese Industrial Standards (JIS) Z8803, specifically, a value measured using an E-type viscometer (e.g., Toki Sangyo Co., Ltd., PE-80L). Furthermore, the viscometer can be calibrated according to JIS Z8809-JS14000.

[0098] The curable composition described above, by combining a compound represented by formula (1) having two (meth)acrylic groups with a compound formed by etherifying at least one terminal hydroxyl group of a polyalkylene glycol, can form a heat storage material with excellent reliability under high temperature and high humidity conditions. The reason for this is that, during the curing of the curable composition, by etherifying the terminal hydroxyl group, the polyalkylene glycol ether, which improves reliability under high temperature and high humidity conditions, can be well incorporated into the cross-linked 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 suitable as a curable composition for forming a heat storage material, and the cured product of the curable composition can be appropriately used as a heat storage material.

[0099] [Heat storage material] One embodiment of the heat storage material includes a hardened form of the hardening component. Figures 1(a) and 1(b) are schematic cross-sectional views showing one embodiment of the heat storage material. As shown in Figure 1(a), one embodiment of the heat storage material 1A is a sheet-like (or film-like) heat storage material including a heat storage layer 2, which is the hardened form of the hardening component.

[0100] As shown in Figure 1(b), another embodiment of the heat storage material 1B is a sheet-like (or film-like) heat storage material comprising a heat storage layer 2, which is a hardened material as the hardening component, 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 attached to the applicable object.

[0101] In each of the embodiments, the thickness of the heat storage layer 2 may be, for example, 0.01 mm or more, 0.05 mm or more, 0.1 mm or more, or 0.2 mm or more, and may be 20 mm or less, 10 mm or less, or 5 mm or less.

[0102] In each of the embodiments described, the heat storage layer 2 may be a hardened material formed by fully hardening the hardening composition, or it may be a hardened material formed by B-stage (semi-hardening) of the hardening composition. In the heat storage material 1A shown in FIG1(a), from the viewpoint that the heat storage material 1A can be suitably attached to the object to which the heat storage material 1A is applied, the heat storage layer 2 is preferably a hardened material formed by B-stage (semi-hardening) of the hardening composition.

[0103] 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, and may be less than 0.03 mm, less than 0.02 mm, or less than 0.015 mm.

[0104] Heat storage material 1A and heat storage material 1B (collectively referred to as heat storage material 1) can be flexibly applied in various fields. For example, heat storage material 1 can be used in air conditioning equipment (improving the efficiency of air conditioning equipment) in automobiles, buildings, public facilities, underground streets, etc., piping in factories, etc. (heat storage of piping), automobile engines (insulation around the engine), electronic components (preventing the overheating of electronic components), underwear fibers, etc.

[0105] The heat storage layer 2 in heat storage material 1A or the heat storage layer 2 and adhesive layer 3 in heat storage layer 1B can be disposed on the support film. That is, another embodiment of the heat storage material may include a support film and a heat storage layer 2 disposed on the support film. Yet another embodiment of the heat storage material may 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. These embodiments of the heat storage material may, for example, be formed in the form of a long strip and wound around a core along its long side (roller-shaped heat storage material).

[0106] 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.

[0107] The thickness of the support membrane 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.

[0108] [Items and their manufacturing methods] Next, regarding articles including heat storage material 1 (a hardened form of a hardening component) and their manufacturing methods, an electronic component that is the object to which the heat storage material 1 is installed will be used as an example for explanation.

[0109] Figures 2(a) and 2(b) are schematic cross-sectional views showing one embodiment of the article and its manufacturing method. In one embodiment of the article manufacturing method, firstly, as shown in Figure 2(a), an electronic component 11A is prepared as the object to which the heat storage material is disposed, i.e., the article. The electronic component 11A includes, for example, a substrate 12 and a semiconductor wafer (heat source) 13 disposed on the substrate 12.

[0110] Then, as shown in FIG2(b), a sheet-like heat storage material 1 is disposed on the substrate 2 and the semiconductor wafer 3 in a manner that makes thermal contact with the substrate 2 and the semiconductor wafer 3, respectively. The heat storage material 1 can be, for example, the heat storage material 1A shown in FIG1(a), or the heat storage material 1B shown in FIG1(b). When using the heat storage material 1B shown in FIG1(b), the heat storage material 1B is disposed in a manner that makes contact with the substrate 12 and the semiconductor wafer 13 through the adhesive layer 3.

[0111] When the heat storage layer in the heat storage material 1 is a hardened material formed by B-stage curing (semi-curing) of a curable component, the heat storage layer is hardened after the heat storage material 1 is disposed. That is, the manufacturing method of the article of this embodiment may further include the step of hardening the heat storage layer of the heat storage material 1 disposed on the substrate 12 and the semiconductor wafer 13.

[0112] This allows for the acquisition of an article 14A comprising a substrate 12, a semiconductor wafer 13, and a heat storage material 1 (a hardened form of a hardening composition) disposed on the substrate 12 and the semiconductor wafer 13.

[0113] In the aforementioned 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.

[0114] Figure 3(a) is a schematic cross-sectional view showing another embodiment of the article. As shown in Figure 3(a), in the article 14B of the other embodiment, 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 portion for which the heat storage material 1 is configured (the portion where the heat storage material 1 contacts the semiconductor wafer 13) is, in Figure 3(a), the side portion of the semiconductor wafer 13, or it can be any surface of the semiconductor wafer 13.

[0115] Figure 3(b) is a schematic cross-sectional view showing another embodiment of the article. As shown in Figure 3(b), in the article 14C of this other embodiment, the heat storage material 1 is disposed on the side of the substrate 12 opposite to the side where the semiconductor wafer 13 is disposed. In this embodiment, although the heat storage material 1 is not in direct contact with the semiconductor wafer 13, it is in thermal contact with the semiconductor wafer 13 through the substrate 12. The location where the heat storage material 1 is disposed can be any surface of the substrate 12 as long as it is in thermal contact with the semiconductor wafer 13. In this case, the heat generated by the heat source (semiconductor wafer) 13 is efficiently conducted to the heat storage material 1 through the substrate 12 and appropriately stored in the heat storage material 1.

[0116] In the manufacturing method of the aforementioned embodiment, the heat storage material 1 is in sheet form. However, in another manufacturing method, a liquid-like hardening composition can also be used to manufacture the article (forming a heat storage material).

[0117] Figures 4(a) to 4(d) are schematic cross-sectional views illustrating another embodiment of the manufacturing method of the article. In this embodiment, as shown in Figure 4(a), an electronic component 11B is first prepared as an object to which a heat storage material is disposed, i.e., an article. The electronic component 11B includes, for example, a substrate (e.g., a circuit board) 12, a semiconductor wafer (heat source) 13 disposed on the substrate 12, and a plurality of connecting portions (e.g., solder) 15 connecting the semiconductor wafer 13 to the substrate 12. The plurality of connecting portions 15 are disposed between the substrate 12 and the semiconductor wafer 13, spaced apart from each other. That is, there is a gap between the substrate 12 and the semiconductor wafer 13 that separates the plurality of connecting portions 15 from each other.

[0118] Then, as shown in FIG4(b), for example, a syringe 16 is used to fill the space between the substrate 12 and the semiconductor wafer 13 with the curing composition 21. The curing composition 21 is the curing composition of the embodiment described above. The curing composition 21 may be in a completely uncured state or in a partially cured state.

[0119] If the curable composition 21 is in a liquid state at room temperature (e.g., 25°C), it can be filled at room temperature. If the curable composition 21 is in a solid state at room temperature, it can be filled after heating the curable composition 21 (e.g., to a temperature above 50°C) to make it into a liquid state.

[0120] By filling the hardening component 21 as described above, as shown in FIG4(c), the hardening component 21 is disposed in the gap between the substrate 12 and the semiconductor wafer 13 in such a way that it is in thermal contact with the substrate 12, the semiconductor wafer 13 and the connecting portion 15 respectively.

[0121] Subsequently, by curing the curable composition 21, as shown in FIG4(d), a hardened material (also referred to as a heat storage layer or heat storage material) 22 of the curable composition can be formed in the gap between the substrate 12 and the semiconductor wafer 13. Thus, an article 14D is 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 hardened material (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.

[0122] When the curing composition 21 contains a thermal polymerization initiator, the curing method for curing the curing composition 21 may be a method of curing the prepared curing composition 21 by heating it. When the curing composition 21 contains a photopolymerization initiator, the curing method for curing the curing composition 21 may be a method of curing the curing composition 21 by irradiating it with light (e.g., light containing at least a portion of wavelengths from 200 nm to 400 nm (ultraviolet light)). The curing method may be any one or a combination of two or more of these methods.

[0123] In each of the embodiments, the heat storage material 1 (the hardened material 22 of the hardened composition) is arranged in a manner that directly contacts the semiconductor wafer 13, which serves as a heat source. However, the heat storage material and the hardened material of the hardened composition only need to be in thermal contact with the heat source. In another embodiment, for example, they can also be arranged in a manner that allows them to be in thermal contact with the heat source via a thermally conductive component (such as a heat dissipation component). [Example]

[0124] The present invention will be described in more detail below by way of embodiments, but the present invention is not limited to the following embodiments.

[0125] [Synthesis of compound (A-1)] A 500 mL flask, including 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 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 acrylamide chloride was added dropwise to the reactor, and the mixture was stirred for 30 minutes. Then, 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 carried out 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. [Chemistry 12]

[0126] [Synthesis of compound (A-2)] Except that 45 g of polyethylene glycol 4,000 (weight average molecular weight: 2700~3300, manufactured by Fujifilm and Koichi Chemical Co., Ltd.) was used instead of 15 g of polyethylene glycol #1000, compound (A-2) with a weight average molecular weight of 3400, represented by the formula (1-3), was obtained in the same manner as compound (A-1).

[0127] [Synthesis of compound (A-3)] Except for replacing 15 g of polyethylene glycol #1000 with 120 g of polyethylene glycol 6,000 (weight average molecular weight: 7300~9300, manufactured by Fujifilm and Hikari Pure Chemical Industries Co., Ltd.), compound (A-3) with a weight average molecular weight of 8000, as described in formula (1-3), was obtained in the same manner as compound (A-1).

[0128] In the embodiments, in addition to compounds (A-1) to (A-3), the following components are also used. (B-1) Polyethylene glycol monomethyl ether (weight average molecular weight: 1000) (B-2) Polyethylene glycol dimethyl ether (weight average molecular weight: 1000) (B-3) Polyethylene glycol monomethyl ether (weight average molecular weight: 4000) (b-1): Polyethylene glycol (weight average molecular weight: 1000) (C-1): Methoxylated polyethylene glycol acrylate (weight average molecular weight: 550) (C-2): Methoxylated polyethylene glycol acrylate (weight average molecular weight: 1000) (D-1) Antioxidant (Adekastab AO-80, manufactured by Adekastab Inc.) (D-2) Polymerization initiator (manufactured with Omnirad 1173 and IGM Resins BV)

[0129] [Production of heat storage materials] The components were mixed at 70°C according to the mixing ratios shown in Tables 1 and 2 to obtain the curable components of the Examples and Reference Examples. Next, at 70°C, using a spacer, the curable components were coated onto a polyethylene terephthalate (PET) film to a cured thickness of 200 μm, and then the PET film was applied to the coated surface. Conversely, a metal halide lamp manufactured by Ushio Electric was used to irradiate the material with ultraviolet (UV) light to achieve an illuminance of 130 mW / cm² and a cumulative luminous intensity of 4000 mJ / cm² or higher, thereby obtaining a heat storage material (a cured product of the curable components).

[0130] Reliability testing under high temperature and high humidity conditions Three 30 mm × 30 mm specimens were cut from each heat storage material (hardened material) of 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 from 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 (Kimwipe, manufactured by Nippon Paper Corporation, Cyprus), 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. Weight change rate (%) = (weight after test - initial weight) / initial weight × 100 In addition, for the remaining samples of the embodiment where no liquid component was detected to have seeped out, the weights (post-test weights) of the three samples were also measured, and the average value of the three samples was calculated based on the weight change rate obtained according to the formula. The weight change rates calculated as described above are shown in Tables 1 and 2.

[0131] [Determination of heat storage] For each heat storage material (hardened material) in the embodiments, the heat storage capacity was calculated using a differential scanning calorimeter (TA Instruments, Discovery DSC250). Specifically, 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, held at -20°C for 3 minutes, and then increased again to 100°C at a rate of 3°C / min. The thermal behavior of each heat storage material was measured. The area of ​​the melting peak was calculated as the heat storage capacity. The results are shown in Tables 1 and 2.

[0132] [Table 1] Reference Example 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 content (parts by weight) A-1 50.0 50.0 - - 50.0 - - A-2 - - 50.0 - - 50.0 - A-3 - - - 50.0 - - 50.0 B-1 - 50.0 50.0 50.0 - - - B-2 - - - - 50.0 50.0 50.0 b-1 50.0 - - - - - - D-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 D-2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Cross-linking density index 2.0 2.0 0.6 0.3 2.0 0.6 0.3 Weight change rate (%) -10.4 -8.6 -2.2 2.6 -10.0 -1.1 1.4 Heat storage (J / g) - 73.8 118.0 134.2 75.9 119.0 140.7

[0133] [Table 2] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 content (parts by weight) A-1 50.0 12.5 25.0 - 10.0 7.5 5.0 A-2 - - - 16.7 - - - A-3 - 12.5 - - 10.0 7.5 5.0 B-1 - 50.0 - - 60.0 70.0 80.0 B-2 - - 50.0 50.0 - - - B-3 50.0 - - - - - - C-1 - - - 22.2 - - - C-2 - 25.0 25.0 11.1 20.0 15.0 10.0 D-1 2.5 2.5 2.5 2.5 2.5 2.5 2.5 D-2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Cross-linking density index 2.0 1.1 1.5 1.2 1.1 1.1 1.1 Rate of change in weight (%) 2.5 3.6 -1.8 1.5 2.1 3.5 2.0 Heat storage (J / g) 84.6 116.6 108.5 120.0 122.5 131.8 135.9

[0134] When the rate of change of weight is negative, it means that the liquid component has seeped to the surface of the sample. 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 to the surface of the sample. It is assumed that the heat storage material absorbs moisture and encapsulates it 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, it can be seen that 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.

[0135] 1, 1A, 1B: Thermal storage materials 2: Heat storage layer 3: Adhesive layer 11A, 11B: Electronic components 12:Substrate 13: Semiconductor wafer (heat source) 14A, 14B, 14C, 14D: Items 15: Connecting part 16: Syringe 21: Hardening components 22: Hardened materials with hardening components (heat storage materials)

Claims

1. A curable composition comprising: a compound represented by formula (1) below; and at least one polyalkylene glycol ether selected from the group consisting of polyalkylene glycol monoalkyl ethers and polyalkylene glycol dialkyl ethers; wherein the compound represented by formula (1) has a weight average molecular weight of 2000 or more.

1. [In formula (1), R11 and R12 independently represent hydrogen atoms or methyl groups, and R13 represents a divalent group having a polyoxyalkylene chain.] 2. The curable composition as claimed in claim 1, comprising a polyalkylene glycol ether having a weight average molecular weight of 400 or more as the polyalkylene glycol ether.

3. The curable composition as claimed in claim 1, comprising a polyalkylene glycol ether having a weight average molecular weight of 5,000 or less as the polyalkylene glycol ether.

4. The curing composition as claimed in claim 1, further comprising a compound represented by formula (3); [Chemical 2] 4. [In formula (3), R31 represents a hydrogen atom or a methyl group, and R32 represents a monovalent group with a polyoxyalkylene chain.] 5. The hardening composition as described in claim 1, used to form a heat storage material.

6. A heat storage material comprising a hardened form of a hardening composition as described in any one of claims 1 to 5.

7. An article comprising: Heat source; And a hardened form of a hardening composition as described in 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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