Hardening compositions, heat storage materials and articles

Abstract

This invention relates to a curable composition, a heat storage material, and an article. The curable composition comprises a compound (1A) represented by formula (1-2) having a Mw of 7000 or more; a compound (1B) represented by formula (1) having a Mw of less than 2000; a compound represented by formula (2); and a polymerization initiator. In formula (1-2), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 14 R represents ethylene, m represents 2 or more such that the molecular weight of the compound represented by formula (1-2) is an integer greater than or equal to 7000. In formula (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 13 This represents a divalent group with a polyoxyalkylene chain. In formula (2), R 21 R represents a hydrogen atom or a methyl group. 22 Let R be the basis represented by the following equation (2-1). In equation (2-1), R 23 R represents oxyethylidene 24 This indicates a hydrogen atom or an alkyl group, n represents an integer greater than 2, and * represents a bond.

Description

[0001] This invention is a divisional application of the invention patent application filed on January 21, 2020, with application number 202080019869.4 and title "Hardenable Composition, Heat Storage Material and Article". Technical Field

[0002] This invention relates to a hardening composition, a heat storage material, and an article. Background Technology

[0003] 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.

[0004] As a method of heat storage, latent heat storage through phase changes of substances can be widely utilized in terms of the amount of heat generated. Water-ice is a well-known latent heat storage material. While water-ice has a high heat output, its phase change temperature is limited to 0°C in atmospheric conditions, thus restricting its applications. Therefore, paraffin wax can be used as a latent heat storage material with a phase change temperature above 0°C and below 100°C. However, if paraffin wax undergoes a phase change upon heating, it becomes liquid, posing a fire hazard. Therefore, for use in heat storage materials, paraffin wax must be stored in sealed containers such as bags to prevent leakage, thus limiting its application.

[0005] Therefore, as a method for improving heat storage materials containing paraffin, for example, a method using a gelling agent is disclosed in Patent Document 1. The gel produced by this method can also maintain a gel-like shape after the phase change of paraffin.

[0006] [Existing Technical Documents]

[0007] [Patent Literature]

[0008] Patent Document 1: Japanese Patent Application Publication No. 2000-109787 Summary of the Invention

[0009] [The problem the invention aims to solve]

[0010] In one aspect, the object of the present invention is to provide a hardenable composition that can form a heat storage material with excellent heat storage properties.

[0011] [Technical means to solve the problem]

[0012] The inventors and others have conducted intensive research and found that the cured material containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups has excellent heat storage properties, that is, the cured composition can form a heat storage material with excellent heat storage properties, thereby completing the present invention. In several aspects, the present invention provides the following [1] to

[14] .

[0013] [1] A curable composition comprising: a compound (1A) represented by the following formula (1-2) having a Mw of 7000 or more; a compound (1B) represented by the following formula (1) having a Mw of less than 2000; a compound represented by the following formula (2); and a polymerization initiator.

[0014]

[0015] In equation (1-2), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 14 [The symbol represents ethylene, and m represents 2 or more such that the molecular weight of the compound represented by formula (1-2) is an integer greater than or equal to 7000.]

[0016]

[0017] 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.

[0018]

[0019] In equation (2), R 21 R represents a hydrogen atom or a methyl group. 22 Let be the basis represented by the following equation (2-1).

[0020]

[0021] In equation (2-1), R 23 R represents oxyethylidene 24 This indicates a hydrogen atom or alkyl group, n represents an integer greater than 2, and * indicates a bond.

[0022] [2] According to the curing composition of [1], wherein the total content of compound (1A) and compound (1B) is 10% by mass or more when the total amount of the curing composition is taken as the basis.

[0023] [3] The hardening composition according to [1] or [2] further contains a heat-retaining component.

[0024] [4] The curing composition according to [3], wherein the heat-retaining component comprises polyalkylene glycol.

[0025] [5] The curing composition according to any one of [1] to [4] further comprises a compound represented by the following formula (3).

[0026]

[0027] In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 Indicates an alkyl group.

[0028] [6] The curing composition according to any one of [1] to [5] further comprises a compound represented by the following formula (4).

[0029]

[0030] In equation (4), R 41 R represents a hydrogen atom or a methyl group. 42 This represents a monovalent group that has a reactive component.

[0031] [7] The curing composition according to [6] further contains a curing agent that can react with the reactive group.

[0032] [8] The hardening composition according to any one of [1] to [7] is used to form a heat storage material.

[0033] [9] A heat storage material comprising a hardened product of a hardening composition according to any one of [1] to [8].

[0034]

[10] An article comprising: a heat source; and a hardened copy of any one of [1] to [8] of a hardening composition disposed in a manner that is in thermal contact with the heat source.

[0035] [The effects of the invention]

[0036] According to one aspect of the present invention, a hardenable composition capable of forming a heat storage material with excellent heat storage properties can be provided. Attached Figure Description

[0037] Figure 1 (a) and (b) are schematic cross-sectional views representing one embodiment of the heat storage material.

[0038] Figure 2 (a) and (b) are schematic cross-sectional views showing one embodiment of the article and its manufacturing method.

[0039] Figure 3(a) and (b) are schematic cross-sectional views representing another embodiment of the article.

[0040] Figure 4 (a) to (d) are schematic cross-sectional views representing another embodiment of the method of manufacturing the article.

[0041] [Explanation of Symbols]

[0042] 1, 1A, 1B: Thermal storage materials

[0043] 2: Heat storage layer

[0044] 3: Adhesive layer

[0045] 11A, 11B: Electronic components

[0046] 12: Substrate

[0047] 13: Semiconductor chip (heat source)

[0048] 14A, 14B, 14C, 14D: Items

[0049] 15: Connecting part

[0050] 16: Syringe

[0051] 21: Hardening composition

[0052] 22: Hardened material of hardening composition (heat storage material) Detailed Implementation

[0053] 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.

[0054] The term "(meth)acryloyl" in this specification refers to "acryloyl" and its corresponding "methacryloyl", and the same applies to similar expressions such as "(meth)acrylate" and "(meth)acrylic acid".

[0055] 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.

[0056] • Measuring machine: HLC-8320GPC (Product name, manufactured by Tosoh Corporation)

[0057] • Analytical column: TSKgel SuperMultipore HZ-H (3-connection) (Product name, manufactured by Tosoh Corporation)

[0058] • Protective column: TSKguardcolumn SuperMP (HZ)-H (Product name, manufactured by Tosoh Corporation)

[0059] • Eluent: Tetrahydrofuran (THF)

[0060] • Measurement temperature: 25℃

[0061] [Curing composition]

[0062] One embodiment of the curable composition contains a compound represented by the following formula (1) and a polymerization initiator.

[0063]

[0064] In equation (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 13 It represents a divalent group with a polyoxyalkylene chain.

[0065] In one implementation, it can be R 11 and R 12 One of them is a hydrogen atom and the other is a methyl group; in another embodiment, it can be R. 11 and R 12 Both of these are hydrogen atoms, and in another embodiment, they can be R. 11 and R 12 Both of these are methyl groups.

[0066] Polyoxyalkylene chains are represented, for example, by the following formula (1-1).

[0067]

[0068] In equation (1-1), R 14 The symbol represents an alkylene group, m represents an integer greater than 2, and * represents a bond.

[0069] R 14 The alkylene groups represented can be linear or branched. 14 For example, it can be an alkylene group having 2 to 4 carbon atoms. Multiple R atoms exist in the polyoxyalkylene chain. 14 They can be the same as each other or different from each other. Multiple R groups exist within the polyoxyalkylene chain. 14 It is preferably selected from one or more of the group consisting of ethylene, propylene, and butylene, more preferably from one or two of the group consisting of ethylene and propylene, and even more preferably all of them are ethylene.

[0070] 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 heat storage can be obtained when m is an integer of 1000 or more, the molecular weight of the compound represented by formula (1) is preferably an integer of 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more or 7000 or more. m can be an integer of 12000 or less, 11000 or less or 10000 or less, representing the molecular weight of the compound represented by formula (1).

[0071] 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.

[0072] The compound represented by formula (1) is preferably the compound represented by the following formula (1-2).

[0073]

[0074] 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.

[0075] From the viewpoint that a heat storage material with superior heat storage capacity can be obtained by having a weight-average molecular weight (Mw) of 1000 or more for the compound represented by formula (1), 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. The weight-average molecular weight (Mw) of the compound represented by formula (1) can be 12000 or less, 11000 or less, or 10000 or less.

[0076] 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.

[0077] In one embodiment, from the viewpoint of obtaining a heat storage material with superior heat storage capacity, the hardening 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, 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.

[0078] When the total amount of the curing composition is taken as a basis, the content of the compound represented by formula (1) may 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, it is preferably 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, the cured product can be folded for use, for example, and therefore the cured product is more suitable as a heat storage material that can be applied to a wider range of uses. When the total amount of the curing composition is taken as a basis, the content of the compound represented by formula (1) may 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), the total amount of these compounds may be within the range described above. When the curing composition contains said compound (1A) and / or said compound (1B), the total amount of compound (1A) and compound (1B) may be within the range, and the individual content of compound (1A) and compound (1B) may be within the range.

[0079] In the case where the curing 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 curing 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) 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 100 parts by mass of the polymeric component.

[0080] There are no particular limitations on the polymerization initiator, which can initiate the polymerization of the compound represented by formula (1) and, as needed, a compound that can copolymerize with the compound represented by formula (1) (details will be described later). For example, the polymerization initiator can be a thermal polymerization initiator that generates free radicals by heat, a photopolymerization initiator that generates free radicals by light, etc.

[0081] 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 may be a curing 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, and may be a curing 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 curing composition can be appropriately selected according to the composition of the curing composition to ensure that the curing composition is appropriately cured.

[0082] Examples of thermal polymerization initiators include: azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylpentanonitrile, azobiscyclohexanone-1-carboxynitrile, azobisbenzoyl, and other azo compounds; and organic peroxides such as benzoyl peroxide, lauroyl peroxide, di-tert-butylperoxide-6-tert-phthalate, tert-butylperoxide-2-ethylhexanoate, 1,1-tert-butylperoxide-3,3,5-trimethylcyclohexane, and tert-butylperoxide-isopropyl carbonate. These thermal polymerization initiators can be used alone or in combination of two or more.

[0083] 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 conditions for light irradiation can be appropriately set depending on the type of photopolymerization initiator.

[0084] 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, benzoyl-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, etc.

[0085] 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: Irgacure 651, manufactured by BASF), and anisole methyl ether. Examples of acetophenone-based photopolymerization initiators include: 1-hydroxycyclohexylphenyl ketone (trade name: Irgacure 184, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one (trade name: Irgacure 2959, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane-1-one (trade name: Irgacure 1173, manufactured by BASF), and methoxyacetophenone, etc.

[0086] 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.

[0087] Examples of benzoin-based photopolymerization initiators include benzoin itself. Examples of benzoyl-based photopolymerization initiators include benzoyl. Examples of benzophenone-based photopolymerization initiators include benzoylbenzoic acid, 3,3'-dimethyl-4-methoxybenzophenone, polyethylene benzophenone, and α-hydroxycyclohexylphenyl ketone. Examples of 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.

[0088] Examples of acylphosphine 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. Acyl)(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)benzyl ... Bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2, 4,6-Trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-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)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.

[0089] The photopolymerization initiator can be used alone or in combination of two or more.

[0090] 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 composition 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).

[0091] The curing composition may further contain a compound that can copolymerize with the compound represented by formula (1). The copolymerizable compound, for example, has a group containing an ethylene unsaturated bond (ethylene unsaturated group). Examples of ethylene unsaturated groups include (meth)acryloyl, vinyl, allyl, etc. The copolymerizable compound is preferably a compound having a (meth)acryloyl group.

[0092] From the viewpoint of obtaining a heat storage material with superior heat storage capacity, the curable composition preferably contains the compound represented by the following formula (2) as the copolymerizable compound.

[0093]

[0094] In equation (2), R 21 R represents a hydrogen atom or a methyl group. 22 This indicates a monovalent group having a polyoxyalkylene chain.

[0095] R 22 For example, it can be a basis represented by the following equation (2-1).

[0096]

[0097] In equation (2-1), R 23 R represents an alkylene group. 24 This indicates a hydrogen atom or an alkyl group, n represents an integer greater than 2, and * represents a bond.

[0098] R 23 The alkylene groups represented can be linear or branched. 23 For example, it can be an alkylene group having 2 to 4 carbon atoms. Multiple R atoms exist in the polyoxyalkylene chain. 23They may be the same as or different from each other. The polyoxyalkylene chain preferably has one or more of the group consisting of oxyethylidene, oxypropylene and oxybutylidene, more preferably has one or two of the group consisting of oxyethylidene and oxypropylene, and even more preferably has only oxyethylidene.

[0099] R 24 The alkyl group represented can be linear or branched. The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 5. 24 Hydrogen atoms or methyl groups are particularly preferred.

[0100] n 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, n is preferably an integer whose molecular weight of the compound represented by formula (2) is 800 or more, 900 or more, or 1000 or more, and more preferably an integer whose molecular weight is 1200 or more, 1400 or more, 1600 or more, 1800 or more, or 2000 or more. n can also be an integer whose molecular weight of the compound represented by formula (2) is 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0101] 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 (2) 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 (2) may be 5000 or less, 4000 or less, 3000 or less, or 2500 or less.

[0102] 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, 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 (2) 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 content of polymeric components of 100 parts by mass.

[0103] From the perspective of adjusting the hardness of the hardened product of the curing composition and from the perspective of making the polymerization initiator easy to dissolve in the curing composition when the polymerization initiator is solid, the curing composition may further contain the compound represented by the following formula (3) as a compound that can be copolymerized with the compound represented by formula (1).

[0104]

[0105] In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 Indicates alkyl group.

[0106] R 32 The alkyl group can be straight-chain or branched. 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.

[0107] The content of the compound represented by formula (3) 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 polymeric components of 100 parts by mass.

[0108] The curing composition may further contain the compound represented by formula (4) as a compound that can be copolymerized with the compound represented by formula (1).

[0109]

[0110] In equation (4), R 41 R represents a hydrogen atom or a methyl group. 42 This indicates a monovalent group that has a reactive group.

[0111] In the case where the curing composition further contains the compound represented by formula (4), after the compound represented by formula (1) and the compound represented by formula (4) (and other compounds that can copolymerize with the compound represented by formula (1)) are polymerized, the reactive group contained in the compound represented by formula (4) reacts with the curing agent described later, thereby further curing the curing composition.

[0112] R 42 The reactive group represented 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 (4) is, for example, a carboxyl-containing compound, a hydroxyl-containing compound, an isocyanate-containing compound, an amino-containing compound or an epoxy-containing compound.

[0113] 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.

[0114] 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.

[0115] Examples of compounds containing isocyanate groups include 2-methacryloyloxyethyl isocyanate and 2-acryloyloxyethyl isocyanate.

[0116] The isocyanate group 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 (4-1).

[0117]

[0118] In the formula, B represents the protecting group, and * represents the bond.

[0119] 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 through deprotection, and the isocyanate group can also react with the curing agent described later.

[0120] 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-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.

[0121] Examples of compounds having a blocked isocyanate group include 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate and 2-(O-[1'-methylpropyleneamino]carboxylamino)methacrylate.

[0122] Examples of amino-containing compounds include: N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, and N,N-diethylaminopropyl methacrylate.

[0123] 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.

[0124] 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 5 parts by mass, relative to the total content of the polymeric components of 100 parts by mass.

[0125] When the total amount of the curing composition is used as a basis, the total content of polymeric components can be 30% or more by mass, 40% or more by mass, 50% or more by mass, 60% or more by mass, 70% or more by mass, 80% or more by mass, or 90% or more by mass, and can be less than 99.9% by mass.

[0126] When the curing composition contains a compound represented by formula (4), 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 (4).

[0127] 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 appropriately selected in the form of a single or a combination of two or more reactive groups contained in the compound represented by formula (4). For example, when the reactive group is an epoxy group, the curing agent is preferably a phenol-based curing agent or an imidazole-based curing agent.

[0128] 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) (diphenylmethane). Aromatic diisocyanates include diisocyanate (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (XDI), tetramethyl xylylene diisocyanate (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, etc.

[0129] Examples of isocyanate-based curing agents include: trimethylene diisocyanate, 1,2-propylidene diisocyanate, butylidene diisocyanate (tetramethylene diisocyanate, 1,2-butylidene diisocyanate, 2,3-butylidene diisocyanate, 1,3-butylidene diisocyanate), 1,5-pentamethylenediisocyanate (PDI), and 1,6-hexamethylenediisocyanate. 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)), the 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.

[0130] 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. 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; phenolic varnish resins containing a furan skeleton; and other phenolic varnish resins.

[0131] 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 dicyandiamine and 1-(o-tolyl)biguanide.

[0132] 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.

[0133] 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, terpineic anhydride, chlorhexidine anhydride, and bicycloheptenedioic anhydride.

[0134] Examples of carboxylic acid-based curing agents include: succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid.

[0135] When the total amount of the curing composition is used as a basis, the content of the curing agent can be more than 0.01% by mass, and can be less than 10% by mass, less than 5% by mass, or less than 1% by mass.

[0136] From the viewpoint of obtaining a heat storage material with superior heat storage capacity, the hardening composition preferably contains heat storage components.

[0137] From the viewpoint that a heat storage material with particularly excellent heat storage capacity can be obtained when used in combination with the compound represented by formula (1), the heat storage component is not easily leached from the hardened material of the hardening composition. It is preferable to include polyalkylene glycol.

[0138] Polyalkylene glycols may be, for example, polyethylene glycol, polypropylene glycol, polybutanediol, etc., with polyethylene glycol being preferred.

[0139] The weight average molecular weight (Mw) of polyalkylene glycols can be above 800, above 900, or above 1000, and can be below 2000, below 1900, or below 1800.

[0140] From the viewpoint that the cured composition can be suitably used as a heat storage material when the curing composition contains the compound represented by formula (2) and a polyalkylene glycol, the melting point of the polyalkylene glycol is preferably close to that of the compound represented by formula (2). The absolute value of the difference between the melting point of the polyalkylene glycol and the melting point of the compound represented by formula (2) is preferably 20°C or less, more preferably 15°C or less, and even more preferably 10°C or less.

[0141] The melting points of the compounds represented by formula (2) and the polyalkylene glycols were determined as follows. Using a differential scanning calorimeter (e.g., PerkinElmer DSC8500), the temperature was increased to 100°C at a rate of 20°C / min, held at 100°C for 3 minutes, then decreased to -30°C at a rate of 10°C / min, held at -30°C for 3 minutes, and then increased back to 100°C at a rate of 10°C / min. The thermal behavior was then measured, and the melting peak was calculated as the melting point.

[0142] From the viewpoint that a heat storage material with superior heat storage can be obtained by having a polyalkylene glycol 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, and even more preferably 60 parts by mass or more. It may also be 70 parts by mass or more, 80 parts by mass or more, 90 parts by mass or more, 100 parts by mass or more, 150 parts by mass or more, 200 parts by mass or more, or 300 parts by mass or more. The content of polyalkylene glycol may be 500 parts by weight or less, 400 parts by weight or less, 300 parts by weight or less, 200 parts by weight or less, 150 parts by weight or less, 120 parts by weight or less, 110 parts by weight or less, or 100 parts by weight or less, relative to the total 100 parts by weight of the polymerizable components. From the viewpoint of excellent flexibility of the cured product of the curing composition, it is preferably 90 parts by weight or less, more preferably 80 parts by weight or less, more preferably 70 parts by weight or less, and particularly preferably 60 parts by weight or less.

[0143] The heat-retaining component can be contained in a hardened composition in the form of a heat-retaining capsule. The heat-retaining capsule has a heat-retaining component and an outer shell (shell) containing the heat-retaining component.

[0144] The heat-retaining component in the heat-retaining capsule may be the aforementioned polyalkylene glycol, or other heat-retaining components. Other heat-retaining components may be appropriately selected, for example, those having a phase transition temperature suitable for the target temperature, depending on the intended use. From the viewpoint of achieving heat retention within a practical range, other heat-retaining components may, for example, have a solid-liquid phase transition point (melting point) exhibiting solid-liquid phase transition within the range of -30°C to 120°C.

[0145] Other heat-retaining components may be chain-like (straight-chain or branched (branched chain)) saturated hydrocarbon compounds (paraffinic hydrocarbon compounds), natural waxes, petroleum waxes, sugar alcohols, etc. From the viewpoint that it is easy to select those 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).

[0146] Specifically, chain-like saturated hydrocarbon compounds can also be n-decane (C10, -29°C), n-undecane (C11, -25°C), n-dodecane (C12, -9°C), n-tridecane (C13, -5°C), n-tetradecane (C14, 6°C), n-pentadecanane (C15, 9°C), n-hexadecane (C16, 18°C), n-heptadecane (C17, 21°C), n-octadecane (C18, 28°C), n-nonadecanane (C19, 32°C), n-eicosane (C20, 37°C), n-ticosane (C10, -29°C), n-undecanane (C10, -25°C), n-dodecane (C12, -9°C), n-tridecane (C13, -5°C), n-tetradecane (C14, 6°C), n-pentadecanane (C15, 9°C), n-hexadecane (C16, 18°C), n-heptadecane (C17, 21°C), n-octadecane (C18, 28°C), n-nonadecanane (C19, 32°C), n-eicosane (C20, 37°C), n-ticosane (C10, -25°C), n-undecan ... 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-decane (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.

[0147] 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, 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.)).

[0148] 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, silica, etc. Examples of microcapsules having an outer shell containing melamine resin include: BA410xxP,6C, BA410xxP,18C, and BA410xxP,37C manufactured by Outlast Technology Co., Ltd.; Thermo Memory FP-16, FP-25, FP-31, and FP-39 manufactured by Mitsubishi Paper Co., 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 silica include Riken resins LA-15, LA-25, and LA-32 manufactured by Riken Industries, Ltd.

[0149] From the viewpoint of further improving the heat storage effect, when taking the total amount of heat storage capsules as a basis, 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.

[0150] For the purpose of adjusting the thermal conductivity, specific gravity, etc. of the capsule, heat-retaining capsules may also contain graphite, metal powder, alcohol, etc. inside the shell.

[0151] 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, and 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)).

[0152] From the viewpoint of further improving the heat storage effect, the content of the heat storage capsule, based on the total amount of the curing 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 suppressing the detachment of the heat storage capsule from the hardened material of the curing composition, the content of the heat storage capsule, based on the total amount of the curing composition, is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less.

[0153] From the viewpoint of improving the thermal reliability of the hardened material (heat storage material) of the hardening composition, the hardening composition preferably contains an antioxidant. Examples of antioxidants include phenolic antioxidants, benzophenone antioxidants, benzoate antioxidants, hindered amine antioxidants, and benzotriazole antioxidants.

[0154] When the total amount of the curing composition is taken as the basis, 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, and can be 10% by mass or less or 5% by mass or less. From the viewpoint that the cured product of the curing composition has excellent softness, it is preferably 4% by mass or less, more preferably 3% by mass or less, more preferably 2.5% by mass or less, and particularly preferably 2% by mass or less.

[0155] The curing composition may further 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 30% by mass or less.

[0156] The curing composition is liquid at 50°C. Therefore, the curing composition can be easily placed in components with complex shapes, etc., by means of 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 based on Japanese Industrial Standards (JIS) Z 8803, specifically a value measured using an E-type viscometer (e.g., Toki Sangyo Co., Ltd., PE-80L). Furthermore, the viscometer can be calibrated based on JIS Z 8809-JS14000.

[0157] The compound represented by formula (1) in the curing composition described above is a compound having a polyoxyalkylene chain and a (meth)acryloyl group. Therefore, the curing composition containing the compound represented by formula (1) and a polymerization initiator can be cured, and the resulting cured product has excellent heat storage capacity due to the polyoxyalkylene chain. Therefore, the curing composition is suitable for use as a curing composition for heat storage materials, and the cured product of the curing composition is suitable for use as a heat storage material.

[0158] Furthermore, the compound represented by formula (1) has two (meth)acryloyl groups, thereby enabling the formation of a cross-linked structure in the resulting cured material. Therefore, when the curing composition contains a heat-retaining component (particularly a polyalkylene glycol) as described above, the cross-linked structure can inhibit the leakage of the heat-retaining component from the cured material. Consequently, the degree of freedom in choosing the heat-retaining component increases, resulting in a further improvement in heat storage capacity.

[0159] [Heat storage material]

[0160] One embodiment of the heat storage material comprises a hardened version of the hardening composition. Figure 1 (a) and (b) are schematic cross-sectional views showing one embodiment of the heat storage material. For example... Figure 1 As shown in (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 a hardened product of the hardening composition.

[0161] like Figure 1 As shown in (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 as a hardened product of the said hardening 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 attached to the object to which the heat storage material 1B is applied.

[0162] 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, or 0.1 mm or more, and may be 20 mm or less, 10 mm or less, or 5 mm or less.

[0163] In each of the embodiments described, the heat storage layer 2 can be a hardened product formed by fully curing the hardening composition, or a hardened product formed by B-stage (semi-curing) of the hardening composition. Figure 1 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 a hardening composition.

[0164] 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.

[0165] 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.

[0166] 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).

[0167] 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.

[0168] The thickness of the support membrane can be, for example, 1 μm or more, 2 μm or more, or 3 μm or more, and can be less than 15 μm, less than 10 μm or less, or less than 7 μm.

[0169] [Items and their manufacturing methods]

[0170] Next, regarding articles including heat storage material 1 (a hardened form of a hardening composition) and methods for manufacturing the same, an electronic component that is the object to which the heat storage material 1 is disposed will be described as an example.

[0171] Figure 2 (a) and (b) are schematic cross-sectional views showing one embodiment of the article and its manufacturing method. In the manufacturing method of the article according to one embodiment, 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.

[0172] Then, as Figure 2 As shown in (b), a sheet-like heat storage material 1 is disposed on the substrate 2 and the semiconductor chip 3 in a manner that allows for thermal contact with both the substrate 2 and the semiconductor chip 3, respectively. The heat storage material 1 can be, for example, the aforementioned... Figure 1 The heat storage material 1A shown in (a) can also be the aforementioned Figure 1 The heat storage material 1B shown in (b) is used. Figure 1 In the case of heat storage material 1B shown in (b), the heat storage material 1B is arranged in such a way that the adhesive layer 3 contacts the substrate 12 and the semiconductor chip 13.

[0173] When the heat storage layer in the heat storage material 1 is a hardened product formed by B-stage curing (semi-curing) of a curing composition, 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 chip 13.

[0174] Thus, an article 14A can be obtained, comprising a substrate 12, a semiconductor chip 13, and a heat storage material 1 (a hardened form of the hardening composition) disposed on the substrate 12 and the semiconductor chip 13.

[0175] 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.

[0176] 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 is configured to contact (in a way of covering) a portion of the exposed surface of the semiconductor chip (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 chip 13) is... Figure 3 (a) can be the side portion of semiconductor chip 13, or any surface of semiconductor chip 3.

[0177] Figure 3 (b) is a schematic cross-sectional view showing another embodiment of the article. For example... Figure 3 As shown in (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, although the heat storage material 1 is not in direct contact with the semiconductor chip 13, it is in thermal contact with the semiconductor chip 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 chip 13. In this case, the heat generated by the heat source (semiconductor chip) 13 is efficiently conducted to the heat storage material 1 through the substrate 12 and appropriately stored in the heat storage material 1.

[0178] 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 may also be used to manufacture the article (forming a heat storage material).

[0179] Figure 4 Views (a) to (d) are schematic cross-sectional views illustrating another embodiment of the method for manufacturing the article. In the manufacturing method of 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 connecting portions (e.g., solder) 15 connecting the semiconductor chip 13 to the substrate 12. The plurality of connecting portions 15 are disposed between the substrate 12 and the semiconductor chip 13, spaced apart from each other. That is, there is a gap between the substrate 12 and the semiconductor chip 13 that separates the plurality of connecting portions 15 from each other.

[0180] Then, as Figure 4 As shown in (b), the curing composition 21 is filled between the substrate 12 and the semiconductor chip 13, for example, using a syringe 16. The curing composition 21 is the curing composition of the embodiment described. The curing composition 21 may be in a completely uncured state or in a partially cured state.

[0181] If the curing composition 21 is in a liquid state at room temperature (e.g., 25°C), it can be filled at room temperature. If the curing composition 21 is in a solid state at room temperature, it can be filled after heating the curing composition 21 (e.g., to a temperature above 50°C) to make it into a liquid state.

[0182] By filling the hardening composition 21 as described above, such as Figure 4As shown in (c), the curing composition 21 is disposed in the gap between the substrate 12 and the semiconductor chip 13 in such a way that it is in thermal contact with the substrate 12, the semiconductor chip 13 and the connecting portion 15 respectively.

[0183] Subsequently, by curing the curing composition 21, such as... Figure 4 As shown in (d), a hardened material (also called a heat storage layer or heat storage material) 22 of a hardened composition can be formed in the gap between the substrate 12 and the semiconductor chip 13. Thus, an article 14D is obtained, which includes: a substrate 12; a semiconductor chip (heat source) 13 disposed on the substrate 12; a plurality of connecting portions 15 connecting the semiconductor chip 13 to the substrate 12; and a hardened material (heat storage layer or heat storage material) 22 of the hardened composition disposed in such a way as to fill the gap formed by the substrate 12, the semiconductor chip (heat source) 13 and the plurality of connecting portions 15.

[0184] The curing method for the curing composition 21, when the curing composition 21 contains a thermal polymerization initiator, can be a method of curing the prepared curing composition 21 by heating it. The curing method for the curing composition 21, when the curing composition 21 contains a photopolymerization initiator, can 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 can be any one or a combination of two or more of these methods.

[0185] In each of the embodiments, the heat storage material 1 (the hardened part of the hardening composition 22) is configured to be in direct contact with the semiconductor chip 13, which is a heat source. However, the heat storage material and the hardened part of the hardening composition only need to be in thermal contact with the heat source. In another embodiment, for example, they can be configured to be in thermal contact with the heat source via a thermally conductive component (a heat dissipation component, etc.).

[0186] [Example]

[0187] The present invention will be described in more detail below by way of examples, but the present invention is not limited to the following examples.

[0188] [Synthesis of compound (A-1)]

[0189] A 500 mL flask, including a stirrer, thermometer, nitrogen inlet tube, outlet tube, and heating mantle, was used as a reactor. 120 g of polyethylene glycol #8000 (weight average molecular weight: 8000, manufactured by Sanyo Chemical Industries, Ltd.) and 300.0 g of toluene were added to the reactor. The mixture was stirred at 250 rpm at 45°C 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. 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 8000.

[0190]

[0191] [Synthesis of compound (A-2)]

[0192] Except that 90 g of polyethylene glycol #6000 (weight average molecular weight: 6000, manufactured by Alfa Aesar) was used instead of 120 g of polyethylene glycol #8000, compound (A-2) with a weight average molecular weight of 6000, represented by the formula (1-3), was obtained in the same manner as compound (A-1).

[0193] [Synthesis of compound (A-3)]

[0194] Except for replacing 120 g of polyethylene glycol #8000 with 60 g of polyethylene glycol #4000 (weight average molecular weight: 4000, manufactured by Sanyo Chemical Industries, Ltd.), compound (A-3) with a weight average molecular weight of 4000, as described in formula (1-3), was obtained in the same manner as compound (A-1).

[0195] [Synthesis of compound (A-4)]

[0196] Except for replacing 120 g of polyethylene glycol #8000 with 30 g of polyethylene glycol #2000 (weight average molecular weight: 2000, manufactured by Sanyo Chemical Industries, Ltd.), compound (A-4) with the weight average molecular weight of 2000, as described in formula (1-3), was obtained in the same manner as compound (A-1).

[0197] [Synthesis of compound (A-5)]

[0198] Except for replacing 120 g of polyethylene glycol #8000 with 15 g of polyethylene glycol #1000 (weight average molecular weight: 1000, manufactured by Sanyo Chemical Industries, Ltd.), compound (A-5) with a weight average molecular weight of 1000, as described in formula (1-3), was obtained in the same manner as compound (A-1).

[0199] In the embodiments, in addition to compounds (A-1) to (A-5), the following components are also used.

[0200] (B-1) Lauroyl peroxide (thermal polymerization initiator)

[0201] (B-2) 2-Hydroxy-2-methyl-1-phenyl-propane-1-one (Photopolymerization initiator, Irgacure 1173 manufactured by BASF)

[0202] (C-1) Methoxylated polyethylene glycol acrylate (weight average molecular weight: 1000, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0203] (C-2) Methoxylated polyethylene glycol acrylate (weight average molecular weight: 1500, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0204] (C-3) Methoxylated polyethylene glycol acrylate (weight average molecular weight: 2000, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

[0205] (C-4) Methyl methacrylate

[0206] (D-1) Polyethylene glycol (weight average molecular weight: 1500, manufactured by Sanyo Chemical Industries, Ltd.)

[0207] (D-2) Polyethylene glycol (weight average molecular weight: 1300, manufactured by Sanyo Chemical Industries, Ltd.)

[0208] (D-3) Polyethylene glycol (weight average molecular weight: 1200, manufactured by Sanyo Chemical Industries, Ltd.)

[0209] (D-4) Heat-retaining capsules (manufactured by Outlast Technology, BA410xxP,37C)

[0210] (E) Phenolic antioxidant (ADEKA STAB AO-80 manufactured by ADEKA (stock))

[0211] [Production of heat storage materials]

[0212] (Examples 1 to 32)

[0213] The components were mixed at 50°C according to the mixing ratios shown in Tables 1 to 3 to obtain a curable composition. Next, the curable composition was coated onto a polyethylene terephthalate (PET) film using a rod coater at 50°C to achieve a cured thickness of 200 μm. The film was then heated at 120°C for 2 hours in an inert gas oven purged with nitrogen to obtain a heat storage material (the cured form of the curable composition).

[0214] (Examples 33-34)

[0215] The components were mixed at 50°C according to the mixing ratios shown in Table 3 to obtain a curable composition. Next, a release PET film was placed on the blue glass with the release surface facing up (opposite to the blue glass). 200 μm thick adhesive tape was used as spacers to adhere the four sides, forming a recess (dam) in the center. The curable composition was placed in the center, and the release PET film was then applied onto the curable composition with the release surface in contact with the curable composition, thus obtaining a laminate. The laminate was then smoothed using a scraper with the surface of the release PET film parallel to the blue glass. A metal halide lamp was then used at an illuminance of 100 mW / cm². 2 Radiation dose: 3000 mJ / cm 2 Under certain conditions, the laminate is irradiated with UV light to obtain a heat storage material (a hardened product of a hardening composition).

[0216] [Evaluation of melting point and heat storage capacity]

[0217] The melting point and heat storage capacity of each heat storage material (hardened material) prepared in the examples were measured using a differential scanning calorimeter (PerkinElmer, model DSC8500). 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 -30°C at a rate of 10°C / min, held at -30°C for 3 minutes, and then increased again to 100°C at a rate of 10°C / min. The thermal behavior was measured. The melting peak value was set as the melting point of the heat storage material, and the area was set as the heat storage capacity. The results are shown in Tables 1 to 3.

[0218] [Evaluation of Flexibility]

[0219] A 200 μm thick heat storage material (a hardened product of the hardening composition) was bent. Flexibility was rated A, and breakage during bending was rated B. The results are shown in Tables 1 to 3.

[0220] [Table 1]

[0221]

[0222] [Table 2]

[0223]

[0224] [Table 3]

[0225]

[0226] As can be seen from the above examples, each hardening composition can form a heat storage material with excellent heat storage capacity.

Claims

1. A hardening composition comprising: The compound (1A) represented by the following formula (1-2) has a Mw of 7000 or more; The compound (1B) represented by the following formula (1) has a Mw of less than 2000; The compound represented by the following formula (2); and Polymerization initiator, In equation (1-2), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 14 The denoting factor is ethylene, and m represents 2 or more such that the molecular weight of the compound represented by formula (1-2) is an integer greater than or equal to 7000. 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. In equation (2), R 21 R represents a hydrogen atom or a methyl group. 22 Let the base be represented by the following equation (2-1), In equation (2-1), R 23 R represents oxyethylidene 24 This indicates a hydrogen atom or an alkyl group, n represents an integer greater than 2, and * represents a bond.

2. The curing composition according to claim 1, wherein the total content of compound (1A) and compound (1B) is 10% by mass or more, based on the total amount of the curing composition.

3. The hardening composition according to claim 1 or 2, further comprising a heat-retaining component.

4. The curable composition according to claim 3, wherein the heat-retaining component comprises polyalkylene glycol.

5. The curing composition according to claim 1 or 2, further comprising a compound represented by formula (3); In equation (3), R 31 R represents a hydrogen atom or a methyl group. 32 Indicates alkyl group.

6. The curing composition according to claim 1 or 2, further comprising a compound represented by formula (4); In equation (4), R 41 R represents a hydrogen atom or a methyl group. 42 This indicates a monovalent group that has a reactive group.

7. The curing composition according to claim 6, further comprising a curing agent capable of reacting with the reactive group.

8. The hardening composition according to claim 1 or 2, used to form a heat storage material.

9. A heat storage material comprising a hardened form of the hardening composition according to any one of claims 1 to 8.

10. An article comprising: Heat source; as well as A hardened product of the hardening composition according to any one of claims 1 to 8, provided in a manner that allows it to be in thermal contact with the heat source.

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