JP7235048B2 - Curable composition, curable composition set, heat storage material, and article - Google Patents

Description

The present invention relates to a curable composition, a curable composition set, a heat storage material, and an article.

A heat storage material is a material from which stored energy can be extracted as heat as needed. This heat storage material is used in applications such as air conditioning equipment, floor heating equipment, refrigerators, electronic parts such as IC chips, automobile interior and exterior materials, automobile parts such as canisters, and heat insulating containers.

As a method for storing heat, latent heat storage using phase change of substances is widely used from the viewpoint of the amount of heat. Water-ice is well known as a latent heat storage material. Water-ice is a substance with a large calorific value, but its phase change temperature is limited to 0° C. in the atmosphere, so its application range is also limited. Therefore, paraffin is used as a latent heat storage material having a phase change temperature higher than 0°C and lower than or equal to 100°C. However, when paraffin undergoes a phase change when heated, it liquefies, and there is a danger of igniting or igniting. are subject to field of application restrictions.

As a method for improving a heat storage material containing paraffin, for example, Patent Document 1 discloses a method using a gelling agent. A gel produced by this method can maintain a gel-like compact even after the phase change of paraffin.

JP-A-2000-109787

An object of the present invention, in one aspect, is to provide a curable composition or a curable composition set that is suitably used for a heat storage material.

［式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はエポキシ基を有する有機基を表す。］
［５］ エポキシ基を有するポリマが、下記式（２）で表される構造単位を更に含む、［４］に記載の硬化性組成物。

［式中、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は炭素数１２～３０のアルキル基、又はポリオキシアルキレン鎖を有する基を表す。］
［６］ 下記式（３）で表される構造単位を含み、エポキシ基を有さないポリマを更に含有する、［１］～［５］のいずれかに記載の硬化性組成物。

［式中、Ｒ^５は水素原子又はメチル基を表し、Ｒ^６は炭素数１２～３０のアルキル基、又はポリオキシアルキレン鎖を有する基を表す。］
［７］ 硬化剤が、フェノール化合物、アミン化合物、酸無水物及びイミダゾール化合物からなる群より選ばれる少なくとも１種である、［１］～［６］のいずれかに記載の硬化性組成物。
［８］ 水を更に含有する、［１］に記載の硬化性組成物。
［９］ エポキシ化合物が水溶性のエポキシ化合物である、［８］に記載の硬化性組成物。
［１０］ 硬化剤が、チオール化合物及びアミン化合物からなる群より選ばれる少なくとも１種である、［８］又は［９］に記載の硬化性組成物。
［１１］ ５０℃において液体状である、［１］～［１０］のいずれかに記載の硬化性組成物。
［１２］ 蓄熱材の形成に用いられる、［１］～［１１］のいずれかに記載の硬化性組成物。
［１３］ ［１］～［１２］のいずれかに記載の硬化性組成物の硬化物を含む、蓄熱材。As a result of extensive research, the present inventors have found that a curable composition or a curable composition set containing a specific component is suitably used for a heat storage material, that is, the curable composition or the curable composition The inventors have found that the heat storage material obtained by using the product set is excellent in heat storage amount, and completed the present invention. In some aspects, the present invention provides the following [1] to [25].
[1] A curable composition containing an epoxy compound, a capsule containing a heat storage component, and a curing agent.
[2] The curable composition of [1], wherein the epoxy compound contains a monomer having an epoxy group.
[3] The curable composition according to [1] or [2], wherein the epoxy compound contains a polymer having an epoxy group.
[4] The curable composition according to [3], wherein the epoxy group-containing polymer contains a structural unit represented by the following formula (1).

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having an epoxy group. ]
[5] The curable composition according to [4], wherein the epoxy group-containing polymer further contains a structural unit represented by the following formula (2).

[In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain. ]
[6] The curable composition according to any one of [1] to [5], which contains a structural unit represented by the following formula (3) and further contains a polymer having no epoxy group.

[In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain. ]
[7] The curable composition according to any one of [1] to [6], wherein the curing agent is at least one selected from the group consisting of phenol compounds, amine compounds, acid anhydrides and imidazole compounds.
[8] The curable composition of [1], which further contains water.
[9] The curable composition of [8], wherein the epoxy compound is a water-soluble epoxy compound.
[10] The curable composition of [8] or [9], wherein the curing agent is at least one selected from the group consisting of thiol compounds and amine compounds.
[11] The curable composition according to any one of [1] to [10], which is liquid at 50°C.
[12] The curable composition according to any one of [1] to [11], which is used for forming a heat storage material.
[13] A heat storage material comprising a cured product of the curable composition according to any one of [1] to [12].

［式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はエポキシ基を有する有機基を表す。］
［１８］ エポキシ基を有するポリマが、下記式（２）で表される構造単位を更に含む、［１７］に記載の硬化性組成物セット。

［式中、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は炭素数１２～３０のアルキル基、又はポリオキシアルキレン鎖を有する基を表す。］
［１９］ 第一液及び第二液の少なくとも一方が、下記式（３）で表される構造単位を含み、エポキシ基を有さないポリマを更に含有する、［１４］～［１８］のいずれかに記載の硬化性組成物セット。

［式中、Ｒ^５は水素原子又はメチル基を表し、Ｒ^６は炭素数１２～３０のアルキル基、又はポリオキシアルキレン鎖を有する基を表す。］
［２０］ 硬化剤が、チオール化合物及びアミン化合物からなる群より選ばれる少なくとも１種である、［１４］～［１９］のいずれかに記載の硬化性組成物セット。
［２１］ 硬化剤がチオール化合物である、［１４］～［１９］のいずれかに記載の硬化性組成物セット。
［２２］ 第一液及び第二液の両方がカプセルを含有する、［１４］～［２１］のいずれかに記載の硬化性組成物セット。
［２３］ 蓄熱材の形成に用いられる、［１４］～［２２］のいずれかに記載の硬化性組成物セット。
［２４］ ［１４］～［２３］のいずれかに記載の硬化性組成物セットにおける、第一液及び第二液の混合物の硬化物を含む、蓄熱材。
［２５］ 熱源と、熱源と熱的に接触するように設けられた、［１３］又は［２４］に記載の蓄熱材と、を備える、物品。[14] A first liquid containing an epoxy compound and a second liquid containing a curing agent, wherein at least one of the first liquid and the second liquid further contains a capsule enclosing a heat storage component. Curable composition set.
[15] The curable composition set of [14], wherein the epoxy compound contains a monomer having an epoxy group.
[16] The curable composition set of [14] or [15], wherein the epoxy compound contains a polymer having an epoxy group.
[17] The curable composition set according to [16], wherein the epoxy group-containing polymer contains a structural unit represented by the following formula (1).

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having an epoxy group. ]
[18] The curable composition set according to [17], wherein the epoxy group-containing polymer further contains a structural unit represented by the following formula (2).

[In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain. ]
[19] Any one of [14] to [18], wherein at least one of the first liquid and the second liquid contains a structural unit represented by the following formula (3) and further contains a polymer having no epoxy group. The curable composition set according to 1.

[In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain. ]
[20] The curable composition set according to any one of [14] to [19], wherein the curing agent is at least one selected from the group consisting of thiol compounds and amine compounds.
[21] The curable composition set according to any one of [14] to [19], wherein the curing agent is a thiol compound.
[22] The curable composition set according to any one of [14] to [21], wherein both the first liquid and the second liquid contain capsules.
[23] The curable composition set according to any one of [14] to [22], which is used for forming a heat storage material.
[24] A heat storage material comprising a cured mixture of the first liquid and the second liquid in the curable composition set according to any one of [14] to [23].
[25] An article comprising a heat source and the heat storage material according to [13] or [24] provided so as to be in thermal contact with the heat source.

According to one aspect of the present invention, it is possible to provide a curable composition or a curable composition set suitable for use as a heat storage material.

FIG. 2 is a schematic cross-sectional view showing an embodiment of a method for forming a heat storage material; FIG. 4 is a schematic cross-sectional view showing another embodiment of a method of forming a heat storage material; FIG. 3 is a schematic cross-sectional view showing another embodiment of an article in which a heat storage material is formed;

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with appropriate reference to the drawings. In addition, this invention is not limited to the following embodiment.

As used herein, "(meth)acryloyl" means "acryloyl" and "methacryloyl" corresponding thereto, and the same applies to similar expressions such as "(meth)acryl".

The weight average molecular weight (Mw) in the present specification means a value measured using gel permeation chromatography (GPC) under the following conditions and determined using polystyrene as a standard substance.
・ Measuring instrument: HLC-8320GPC (product name, manufactured by Tosoh Corporation)
・ Analysis column: TSKgel SuperMultipore HZ-H (three connected) (product name, manufactured by Tosoh Corporation)
Guard column: TSKguardcolumn SuperMP (HZ)-H (product name, manufactured by Tosoh Corporation)
・ Eluent: THF
・Measurement temperature: 25°C

[Curable composition]
A curable composition according to one embodiment contains an epoxy compound, a capsule containing a heat storage component (hereinafter also referred to as a “heat storage capsule”), and a curing agent.

The epoxy compound may contain a monomer having an epoxy group.

The monomer having an epoxy group may be, for example, a monomer having an epoxy group and an aromatic ring, and is a compound obtained by glycidylating the amino group and hydroxyl group of a compound having one or both of an amino group and a hydroxyl group and an aromatic ring. (Glycidylate).

Monomers having an epoxy group and an aromatic ring include biphenyl-type epoxy resins (e.g., "jER (registered trademark) YX4000" (trade name, manufactured by Mitsubishi Chemical Corporation)) and brominated epoxy resins (e.g., "BROC"). , and “BR-250H” (both trade names, manufactured by Nippon Kayaku Co., Ltd.). A monomer having an epoxy group and an aromatic ring may be a heteroaromatic epoxy resin such as a triazine skeleton-containing epoxy resin.

Examples of glycidyl compounds of compounds having an amino group and an aromatic ring (also called aromatic glycidylamine-type epoxy compounds) include tetraglycidyldiaminodiphenyl ether, tetraglycidyltetramethyldiaminodiphenyl ether, tetraglycidyltetraethyldiaminodiphenyl ether, tetraglycidylbis(amino phenoxyphenyl)propane, tetraglycidylbis(aminophenoxyphenyl)sulfone, tetraglycidylbis(trifluoromethyl)diaminobiphenyl, tetraglycidylbenzidine, tetraglycidyltolysine, tetraglycidyl-p-phenylenediamine, tetraglycidyl-m-phenylenediamine, 1:4 addition reaction formation of tetraglycidyldiaminotoluene, tetraglycidyldiaminoxylene, tetraglycidyldiaminodiphenylsulfone, tetraglycidyldiaminodiphenylmethane, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene and epichlorohydrin things, etc. Commercially available aromatic glycidylamine epoxy compounds include "ELM434" (trade name, manufactured by Sumitomo Chemical Co., Ltd.), "Araldite (registered trademark) MY720", "Araldite MY721", "Araldite MY722", “Araldite MY9512”, “Araldite MY9612”, “Araldite MY9634”, “Araldite MY9663” (trade names, manufactured by Huntsman Japan Co., Ltd.), “jER (registered trademark) 604” (trade name, Mitsubishi Chemical Corporation ), “TGDAS” (both trade names, manufactured by Konishi Chemical Industry Co., Ltd.), and the like.

Examples of glycidylates of compounds having a hydroxyl group and an aromatic ring include tetraglycidylates of tetravalent naphthol intermediates (also called naphthalene-type epoxy compounds), which are condensates of dihydroxynaphthalene and formaldehyde. Commercially available naphthalene-type epoxy compounds include "Epiclon (registered trademark) HP4700", "Epiclon HP4710", and "Epiclon HP4770" (trade names, manufactured by DIC Corporation).

Glycidylated products of compounds having an amino group and a hydroxyl group and an aromatic ring (also called aminophenol-type epoxy compounds) include p-aminophenol, m-aminophenol, p-aminocresol, trifluoromethylhydroxyaniline, and hydroxyphenyl. Examples include triglycidyl compounds of aniline, methoxyhydroxyaniline, butylhydroxyaniline, hydroxynaphthylaniline, and the like. Commercial products of aminophenol-type epoxy compounds include "ELM120", "ELM100" (trade names, manufactured by Sumitomo Chemical Co., Ltd.), "Araldite (registered trademark) MY0500", and "Araldite MY0510" (trade names, , Huntsman Japan Co., Ltd.), "jER (registered trademark) 630" (both trade names, manufactured by Mitsubishi Chemical Corporation), and the like.

Epoxy compounds may include polymers having epoxy groups.

式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はエポキシ基を有する有機基を表す。Ｒ^２は、好ましくはグリシジル基である。In one embodiment, the epoxy group-containing polymer may be a polymer (polymer (A)) containing a structural unit represented by the following formula (1).

In the formula, ^R1 represents a hydrogen atom or a methyl group, and ^R2 represents an organic group having an epoxy group. R ² is preferably a glycidyl group.

The content of the structural unit represented by formula (1) in the polymer (A) is 2 parts by mass or more, or 95 parts by mass or less with respect to 100 parts by mass of all structural units constituting the polymer (A). good.

式中、Ｒ^３は水素原子又はメチル基を表し、Ｒ^４は炭素数１２～３０のアルキル基、又はポリオキシアルキレン鎖を有する基を表す。The polymer (A) further contains a structural unit represented by the following formula (2) in addition to the structural unit represented by the formula (1), from the viewpoint of further improving the heat storage property when forming the heat storage material. you can stay

In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain.

When R ⁴ is an alkyl group, the alkyl group may be linear or branched. The number of carbon atoms in the alkyl group represented by R ⁴ is preferably 12-28, more preferably 12-26, even more preferably 12-24, particularly preferably 12-22. Examples of alkyl groups represented by ^R4 include dodecyl group (lauryl group), tetradecyl group, hexadecyl group), octadecyl group (stearyl group), docosyl group (behenyl group), tetracosyl group, hexacosyl group, octacosyl group, and the like. is mentioned. The alkyl group represented by ^R4 is preferably at least one selected from the group consisting of dodecyl group (lauryl group), hexadecyl group, octadecyl group (stearyl group) and docosyl group (behenyl group).

式中、Ｒ^ａは水素原子又は炭素数１～１８のアルキル基を表し、ｍは２～４の整数を表し、ｎは２～９０の整数を表し、＊は結合手を表す。Ｒ^４で表される基に複数存在する（ＣＨ_２）_ｍは、互いに同一でも異なっていてもよい。つまり、Ｒ^４で表されるポリオキシアルキレン鎖を有する基は、ポリオキシエチレン鎖、ポリオキシプロピレン鎖及びポリオキシブチレン鎖のいずれか一種のみを有していてよく、二種以上を有していてもよい。When R ⁴ is a group having a polyoxyalkylene chain, the group having a polyoxyalkylene chain is a group represented by the following formula (4), i.e., a polyoxyethylene chain, a polyoxypropylene chain and a polyoxybutylene chain. It may be a group having at least one polyoxyalkylene chain selected from the group consisting of.

In the formula, R ^a represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, m represents an integer of 2 to 4, n represents an integer of 2 to 90, and * represents a bond. Plural (CH ₂ ) _m present in the group represented by R ⁴ may be the same or different. That is, the group having a polyoxyalkylene chain represented by ^R4 may have only one of a polyoxyethylene chain, a polyoxypropylene chain and a polyoxybutylene chain, and may have two or more. may

The alkyl group represented by ^Ra may be linear or branched. The number of carbon atoms in the alkyl group represented by R ^a is preferably 1-15, more preferably 1-10, still more preferably 1-5. ^Ra is particularly preferably a hydrogen atom or a methyl group.

m is preferably 2 or 3, more preferably 2. n is preferably an integer of 4 to 80, 6 to 60, 9 to 40, 9 to 30, 10 to 30, 15 to 30, or 15 to 25 from the viewpoint of further improving the heat storage amount of the heat storage material.

When the polymer (A) contains the structural unit represented by formula (2), the content of the structural unit represented by formula (2) is based on 100 parts by mass of all structural units constituting the polymer (A) , preferably 60 parts by mass or more, more preferably 80 parts by mass or more, and may be, for example, 98 parts by mass or less.

The weight average molecular weight of the polymer (A) is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 40,000 or less, and may be, for example, 5,000 or more.

In another embodiment, the polymer having an epoxy group is a bisphenol A type epoxy resin (e.g., "jER (registered trademark) 828" (trade name, manufactured by Mitsubishi Chemical Corporation)), a bisphenol F type epoxy resin (e.g., , "jER (registered trademark) 807" (trade name, manufactured by Mitsubishi Chemical Corporation)), phenolic novolac type epoxy resin (e.g., "jER (registered trademark) 152" (trade name, manufactured by Mitsubishi Chemical Corporation)) , cresol novolak type epoxy resin (e.g., "Epiclon (registered trademark) N660" (trade name, manufactured by DIC Corporation)), dicyclopentadiene type epoxy resin (e.g., "Epiclon (registered trademark) GP7200" (trade name, Aromatic epoxy resins such as those manufactured by DIC Corporation) may also be used.

In another embodiment, the polymer having an epoxy group is an aliphatic glycidyl ether type epoxy resin such as an alkyl diglycidyl ether type epoxy resin (for example, "YED216" (trade name, manufactured by Mitsubishi Chemical Corporation)), It may also be a non-aromatic epoxy resin such as a cyclic glycidyl ether epoxy resin.

The epoxy compounds described above may be used singly or in combination of two or more. The above-described epoxy group-containing polymer is combined with a monovalent epoxy group-containing compound (e.g., "jER (registered trademark) 801" (trade name, manufactured by Mitsubishi Chemical Corporation)) for viscosity adjustment and the like. may be used

The content of the epoxy compound described above is preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the curable composition, from the viewpoint of suppressing the heat storage capsules from falling off from the cured product of the curable composition. % or more, more preferably 20 mass % or more, and from the viewpoint of further improving heat storage properties, it is preferably 60 mass % or less, more preferably 50 mass % or less, and still more preferably 35 mass % or less.

A capsule enclosing a heat storage component (heat storage capsule) has a heat storage component and a shell enclosing the heat storage component. The heat-accumulating component may be any component that can store heat, and may be, for example, a component that has heat-accumulating properties associated with phase transition. As the heat storage component, one having a phase transition temperature suitable for the target temperature is appropriately selected according to the purpose of use. The heat accumulating component has a solid/liquid phase transition point (melting point) at -30 to 120° C., for example, from the viewpoint of obtaining a heat accumulating effect within a practical range.

The heat storage component is, for example, a chain saturated hydrocarbon compound (paraffinic hydrocarbon compound), natural wax, petroleum wax, polyethylene glycol, organic compound such as sugar alcohol, or inorganic compound hydrate, crystal structure change. It may be an inorganic compound such as an inorganic compound showing The heat storage component is preferably a chain saturated hydrocarbon compound (paraffinic hydrocarbon compound) from the viewpoint of being inexpensive, having low toxicity, and having a desired phase transition temperature that can be easily selected. In this specification, the term "chain" means linear or branched (branched).

Chain saturated hydrocarbon compounds, specifically, n-decane (C10 (carbon number, hereinafter the same), −29 ° C. (transition point (melting point), hereinafter the same)), n-undecane (C11, −25 ℃), n-dodecane (C12, -9 ℃), n-tridecane (C13, -5 ℃), n-tetradecane (C14, 6 ℃), n-pentadecane (C15, 9 ℃), n-hexadecane (C16 , 18°C), n-heptadecane (C17, 21°C), n-octadecane (C18, 28°C), n-nanodecane (C19, 32°C), n-eicosane (C20, 37°C), n-henicosane (C21 , 41°C), n-docosane (C22, 46°C), n-tricosane (C23, 47°C), n-tetracosane (C24, 50°C), n-pentacosane (C25, 54°C), n-hexacosane (C26 , 56°C), n-heptacosane (C27, 60°C), n-octacosane (C28, 65°C), n-nonacosane (C29, 66°C), n-triacontane (C30, 67°C), n-tetracontane (C40, 81°C), n-pentacontane (C50, 91°C), n-hexacontane (C60, 98°C), n-hectane (C100, 115°C), and the like. The chain saturated hydrocarbon compound may be a branched saturated hydrocarbon compound having the same number of carbon atoms as these linear saturated hydrocarbon compounds. The chain saturated hydrocarbon compound may be one or more of these.

The outer shell (shell) enclosing these heat accumulating components is preferably made of a material having a heat resistant temperature sufficiently higher than the transition point (melting point) of the heat accumulating components. The material forming the outer shell has a heat resistant temperature of, for example, 30° C. or higher, preferably 50° C. or higher, relative to the transition point (melting point) of the heat storage component. The heat resistant temperature is defined as the temperature at which the weight of the capsule decreases by 1% when the weight decrease of the capsule is measured using a simultaneous differential thermal thermogravimetric analyzer (eg, TG-DTA6300 (manufactured by Hitachi High-Tech Science Co., Ltd.)). be done.

As a material for forming the outer shell, a material having a strength corresponding to the application of the heat storage material formed from the curable composition is appropriately selected. The shell may preferably be made of melamine resin, acrylic resin, urethane resin, silica, or the like. Examples of microcapsules having an outer shell made of melamine resin include BA410xxP, 18C, BA410xxP, 37C manufactured by Outlast Technology Co., Ltd.; FP-39, Riken Resin PMCD-15SP, 25SP, 32SP manufactured by Miki Riken Kogyo Co., Ltd. are exemplified. Examples of microcapsules having outer shells made of acrylic resin (polymethyl methacrylate resin) include Micronal DS5001X and 5040X manufactured by BASF. Examples of microcapsules having an outer shell made of silica include RIKEN RESIN LA-15, LA-25, LA-32 manufactured by Miki Riken Kogyo Co., Ltd., and the like.

The content of the heat storage component is preferably 20% by mass or more, more preferably 60% by mass or more, based on the total amount of the heat storage capsule, from the viewpoint of further enhancing the heat storage effect. From the viewpoint of suppressing, it is preferably 80% by mass or less.

The heat storage capsule may further contain graphite, metal powder, alcohol, etc. in the outer shell for the purpose of adjusting the thermal conductivity, specific gravity, etc. of the capsule.

The particle size (average particle size) of the heat storage capsule is preferably 0.1 µm or more, more preferably 0.2 µm or more, more preferably 0.5 µm or more, and preferably 100 µm or less, more preferably 50 µm or less. . The particle size (average particle size) of the heat storage capsule is measured using a laser diffraction particle size distribution analyzer (for example, SALD-2300 (manufactured by Shimadzu Corporation)).

The heat storage capacity of the heat storage capsule (powder state) is preferably 150 J/g or more from the viewpoint of obtaining a heat storage material having a higher heat storage density. Heat storage capacity is measured by differential scanning calorimetry (DSC).

Regarding the method for producing the heat-storage capsule, conventionally known production methods such as an interfacial polymerization method, an in-situ polymerization method, an in-liquid hardening coating method, a coacervate method, etc. are appropriately selected according to the heat-storage component, outer shell material, and the like. method should be selected.

The content of the heat storage capsules is preferably 40% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass or more based on the total amount of the curable composition, from the viewpoint of further enhancing the heat storage effect. The content of the heat storage capsules is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of suppressing the heat storage capsules from falling off from the cured product of the curable composition. is.

A curing agent is a curing agent that reacts with the epoxy group of the epoxy compound described above. The curing agent is preferably a thermosetting agent that undergoes a curing reaction with the epoxy compound by heat. When the curing agent is a heat curing agent, the epoxy compound and the curing agent react with each other by applying heat of, for example, 50° C. or higher to the curable composition to obtain a cured product of the curable composition.

When a thermosetting agent is used, the curable composition is preferably a curable composition that is cured by heating at 100° C. or higher, more preferably 105° C. or higher, and even more preferably 110° C. or higher. It may be a curable composition that is cured by heating at 200° C. or lower, 180° C. or lower, or 170° C. or lower. The heating time for heating the curable composition may be appropriately selected according to the composition of the curable composition so that the curable composition is suitably cured.

The curing agent is more preferably at least one selected from the group consisting of phenol compounds, amine compounds, acid anhydrides and imidazole compounds.

Examples of phenol compounds 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′-biphenol, 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′-butylidene-bis(3-methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol , hydroquinone, pyrogallol, phenolic compounds having a diisopropylidene skeleton; phenolic compounds having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; cresol compounds; ethylphenol compounds; butylphenol compounds; octylphenol compounds; Novolak resins made from various phenols such as bisphenol F, bisphenol S, and naphthol compounds, xylylene skeleton-containing phenol novolac resins, dicyclopentadiene skeleton-containing phenol novolac resins, biphenyl skeleton-containing phenol novolac resins, fluorene skeleton-containing phenol novolac resins, furan Various novolac resins such as skeleton-containing phenolic novolac resins can be used.

Examples of amine compounds include aromatic amines such as diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene and m-xylylenediamine; Aliphatic amines such as diethylaminopropylamine, diethylenetriamine, isophoronediamine, bis(4-amino-3-methyldicyclohexyl)methane, polyetherdiamine; guanidine compounds such as dicyandiamide and 1-(o-tolyl)biguanide; amine adducts, ketimine and modified amines such as

Examples of acid anhydrides include aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol trimellitic anhydride, and biphenyltetracarboxylic anhydride. Carboxylic acid anhydrides; aliphatic carboxylic acid anhydrides such as azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nadic acid anhydride, het acid anhydride, hymic acid anhydride and alicyclic carboxylic acid anhydrides such as

Examples of imidazole compounds include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl -2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 2,3-dihydro-1H -pyrrolo-[1,2-a]benzimidazole, 2,4-diamino-6(2'-methylimidazole (1'))ethyl-s-triazine, 2,4-diamino-6(2'-undecyl imidazole (1′))ethyl-s-triazine, 2,4-diamino-6(2′-ethyl-4-methylimidazole(1′))ethyl-s-triazine, 2,4-diamino-6(2′) -methylimidazole (1′)) ethyl-s-triazine isocyanurate, 2-methylimidazole isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-3,5-dihydroxymethylimidazole, 2 -phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.

Curing agents may be used alone or in combination of two or more. The content of the curing agent, based on the total amount of the curable composition, is preferably 0.01% by mass or more, and is preferably 45% by mass or less, more preferably 40% by mass or less, and still more preferably 35% by mass or less. is.

式中、Ｒ^５は水素原子又はメチル基を表し、Ｒ^６は炭素数１２～３０のアルキル基、又はポリオキシアルキレン鎖を有する基を表す。From the viewpoint of further enhancing the heat storage effect, the curable composition is a polymer containing a structural unit (structural unit (A)) represented by the following formula (3) (hereinafter also referred to as “heat storage (meth)acrylic polymer”). ) may be further contained. A polymer containing structural units (A) is a polymer having no epoxy group in the molecule.

In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain.

The alkyl group represented by R ⁶ or the group having a polyoxyalkylene chain is the same group as the alkyl group represented by R ⁴ in the above formula (2) or the group having a polyoxyalkylene chain, good.

The content of the structural unit (A) is preferably 60 parts by mass or more, more preferably 60 parts by mass or more, based on 100 parts by mass of all the structural units constituting the heat-storage (meth)acrylic polymer, from the viewpoint of further improving the heat storage capacity of the heat storage material. is 80 parts by mass or more, and may be, for example, 98 parts by mass or less.

The weight average molecular weight of the heat storage (meth)acrylic polymer is preferably 100,000 or less, more preferably 70,000 or less, still more preferably 40,000 or less, and may be, for example, 5,000 or more.

When the curable composition contains a heat storage (meth)acrylic polymer, the content thereof is preferably 10% by mass or more, more preferably 20% by mass, based on the total amount of the curable composition, from the viewpoint of further enhancing the heat storage effect. % or more, more preferably 30 mass % or more, and from the viewpoint of handling properties, preferably 50 mass % or less, more preferably 40 mass % or less, and even more preferably 35 mass % or less.

The curable composition can further contain other additives, if desired. Other additives include, for example, curing accelerators, antioxidants, coloring agents, fillers, crystal nucleating agents, heat stabilizers, heat conducting agents, plasticizers, foaming agents, flame retardants, damping agents, flame retardant aids, agents (for example, metal oxides) and the like. Other additives may be used singly or in combination of two or more. The content of other additives may be, for example, 0.1% by mass or more and 30% by mass or less based on the total amount of the curable composition.

The curable composition may be liquid at 50°C. Thereby, the curable composition can be easily provided by a method such as filling even between members having a complicated shape. When the curable composition does not contain a heat-storage (meth)acrylic polymer, the curable composition may be liquid at room temperature (eg, 25°C).

The viscosity of the curable composition at 50° C. is preferably 100 Pa·s or less, more preferably 80 Pa·s or less, still more preferably 60 Pa·s or less, and particularly preferably 50 Pa·s, from the viewpoint of excellent fluidity and handling properties. It is below. The viscosity of the curable composition at 50° C. may be, for example, 0.5 Pa·s or more.

The viscosity of the curable composition means a value measured based on JIS Z 8803, specifically, E-type viscometer (e.g., manufactured by Toki Sangyo Co., Ltd., PE-80L) was measured. means value. The viscometer can be calibrated according to JIS Z 8809-JS14000.

The curable composition may further contain water as another embodiment. By diluting the curable composition with water to such an extent that the epoxy compound and the curing agent do not react with each other, the curable composition can be stored in an uncured state for a certain period of time. After the curable composition containing water is placed on the object on which the heat storage material is to be provided by filling, coating, or the like, the water is volatilized, thereby allowing the epoxy compound and the curing agent to react with each other without heating. A cured product of the curable composition can be obtained.

If the curable composition contains water, the epoxy compound is preferably a water-soluble epoxy compound.

A water-soluble epoxy compound may be, for example, a glycidyl ether compound. A glycidyl ether compound may be, for example, a compound in which some or all of the hydrogen atoms in the hydroxyl groups of a polyhydric alcohol are substituted with glycidyl groups. The polyhydric alcohol may be, for example, a dihydric alcohol such as ethylene glycol, diethylene glycol, polyethylene glycol, or polypropylene glycol, a trihydric alcohol such as glycerol, or a tetrahydric or higher alcohol such as sorbitol or polyglycerol. There may be.

Examples of water-soluble epoxy compounds (glycidyl ether compounds) include glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol di glycidyl ether and the like. These glycidyl ether compounds may be used singly or in combination of two or more.

The polyhydric alcohol that constitutes the glycidyl ether compound may be linear or branched, and is preferably linear from the viewpoint of excellent flexibility when the heat storage material is formed. From the same point of view, the content of the glycidyl ether compound composed of a linear polyhydric alcohol is preferably 30% by mass or more based on the total amount of the epoxy compound.

式中、ｎは１～２２の整数を表す。ｎ（重合度）は、好ましくは、１～１３、１～９、１～５、１０～２２、１４～２２、又は１８～２２の整数であってよく、１又は２２であってもよい。The water-soluble epoxy compound is preferably ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether (collectively referred to as "(poly)ethylene glycol (also referred to as "diglycidyl ether"), more preferably a compound represented by the following formula (5).

In the formula, n represents an integer of 1-22. n (degree of polymerization) is preferably an integer of 1 to 13, 1 to 9, 1 to 5, 10 to 22, 14 to 22, or 18 to 22, and may be 1 or 22.

When a water-soluble epoxy compound is used as the epoxy compound, the curing agent used in the curable composition may be a curing agent that can react at room temperature (for example, 25°C). Such a curing agent may be, for example, at least one selected from the group consisting of thiol compounds and amine compounds.

Examples of thiol compounds include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3 - mercaptobutyrate), trimethylol ethane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoglycolate), butanediol bis (3-mercaptoglycolate), trimethylol propane tris (3-mercaptoglycolate) ), pentaerythritol tetrakis (3-mercaptoglycolate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto propionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) (e.g., "Kalenz MT-PE1" (trade name, manufactured by Showa Denko K.K.) ), 1,4-bis(3-mercaptobutyryloxy)butane (for example, “Karenzu MT-BD1” (trade name, manufactured by Showa Denko Co., Ltd.)), 1,3,5-tris (3-mel Kabutobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (for example, “Karenzu MT-NR1” (trade name, manufactured by Showa Denko K.K.)) etc.

Amine compounds include aliphatic amines such as ethylenediamine, diethylenetriamine, dipropylenediamine, hexamethylenediamine, octanediamine, triethylenetetramine, and N-aminoethylpiperazine.

Aspects of the water-containing curable composition other than the components described above may be the same as those of the curable composition according to the embodiment described above.

[Curable composition set]
A curable composition set according to one embodiment comprises a first liquid containing the above-described epoxy compound and a second liquid containing a curing agent, and at least one of the first liquid and the second liquid is the above-described It further contains a capsule (heat-storage capsule) enclosing a heat-storage component. Since the aspects of the epoxy compound and the heat storage capsules are the same as those used in the curable composition, description thereof is omitted.

That is, in the curable composition set, the first liquid may contain an epoxy compound, and may contain an epoxy compound and heat storage capsules. The second liquid may contain a curing agent, and may contain a curing agent and heat storage capsules. The curable composition set preferably comprises a first liquid containing the epoxy compound and the heat storage capsules, and a second liquid containing the curing agent and the heat storage capsules.

By mixing the first liquid and the second liquid, the epoxy compound and the curing agent react to obtain a cured product of the mixture of the first liquid and the second liquid (curable composition). According to the curable composition set according to the present embodiment, by mixing the first liquid and the second liquid, a cured product of the mixture (curable composition) of the first liquid and the second liquid can be obtained immediately. . That is, in the curable composition set according to this embodiment, the mixture (curable composition) containing the epoxy compound can be cured at a high rate.

The content of the epoxy compound is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 15% by mass or more, based on the total amount of the first liquid, from the viewpoint of suppressing the heat storage capsules from falling off from the cured product of the curable composition. The content is preferably 20% by mass or more, and from the viewpoint of further improving heat storage properties, it is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less. From the same point of view, the content of the epoxy compound is preferably 5% by mass or more, more preferably 7% by mass or more, and still more preferably 10% by mass or more, based on the total amount of the first liquid and the second liquid. Also, it is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less.

The content of the heat storage capsules (the total content of the heat storage capsules contained in the first liquid and the second liquid) is the total amount of the first liquid and the second liquid from the viewpoint of further enhancing the heat storage effect of the heat storage material. As a standard, it is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more. The content of the heat storage capsules is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of suppressing the heat storage capsules from falling off from the cured product of the curable composition. is.

The curing agent contained in the second liquid is preferably a curing agent that can react with the epoxy compound at room temperature (for example, 25°C). The curing agent is more preferably at least one selected from the group consisting of thiol compounds and amine compounds. The curing agent is more preferably a thiol compound.

Examples of thiol compounds include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3 - mercaptobutyrate), trimethylol ethane tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoglycolate), butanediol bis (3-mercaptoglycolate), trimethylol propane tris (3-mercaptoglycolate) ), pentaerythritol tetrakis (3-mercaptoglycolate), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto propionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate) (e.g., "Kalenz MT-PE1" (trade name, manufactured by Showa Denko K.K.)) , 1,4-bis(3-mercaptobutyryloxy)butane (for example, "Karenzu MT-BD1" (trade name, manufactured by Showa Denko KK)), 1,3,5-tris(3-mercaptobutyl oxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (for example, "Karenzu MT-NR1" (trade name, manufactured by Showa Denko K.K.)) and the like. be done.

Amine compounds include aliphatic amines such as ethylenediamine, diethylenetriamine, dipropylenediamine, hexamethylenediamine, octanediamine, triethylenetetramine, and N-aminoethylpiperazine.

The content of the curing agent is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 90% by mass or less, based on the total amount of the second liquid. is 85% by mass or less, more preferably 80% by mass or less. The content of the curing agent is preferably 0.01% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 0.01% by mass or more, based on the total amount of the first liquid and the second liquid. Preferably, it is 20% by mass or less.

In the curable composition set, at least one of the first liquid and the second liquid further contains a polymer (heat-storage (meth)acrylic polymer) containing the structural unit (A) represented by the formula (3) described above. may Since the aspect of the structural unit (A) is the same as described above, the description is omitted.

When the second liquid contains a heat-storing (meth)acrylic polymer, the heat-storing (meth)acrylic polymer in the second liquid may further contain a structural unit having a reactive group (structural unit (B)). .

The reactive group possessed by the structural unit (B) is a group capable of reacting with a curing agent (the curing agent described above or the second curing agent described later), for example, at least one selected from the group consisting of a carboxyl group and a hydroxyl group. It is one type of group.

式中、Ｒ^７は水素原子又はメチル基を表し、Ｒ^８は水素原子又は反応性基を有する有機基を表す。Ｒ^８で表される反応性基は、上述した反応性基であってよい。Structural unit (B) is preferably a structural unit represented by the following formula (6).

In the formula, ^R7 represents a hydrogen atom or a methyl group, and ^R8 represents a hydrogen atom or an organic group having a reactive group. The reactive groups represented by R ⁸ may be the reactive groups described above.

When the heat-storage (meth)acrylic polymer contains the structural unit (B), the content of the structural unit (B) is adjusted to the heat-storage (meth)acrylic polymer from the viewpoint of obtaining a further excellent heat storage amount when forming the heat storage material. It may be 2 parts by mass or more and may be 25 parts by mass or less, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 100 parts by mass of all structural units constituting the polymer. 13 parts by mass or less, particularly preferably 10 parts by mass or less.

In the curable composition set, when at least one of the first liquid and the second liquid contains a heat-storage (meth)acrylic polymer, the content (the heat-storage (meth)acrylic polymer contained in the first and second liquids From the viewpoint of further enhancing the heat storage effect, the total polymer content) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass, based on the total amount of the first liquid and the second liquid. % by mass or more, and from the viewpoint of handling properties, it is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.

When the second liquid contains a heat-storage (meth)acrylic polymer having the structural unit (B), the first liquid suppresses leakage and volatilization of the heat storage material and improves heat resistance. It may further contain a curing agent (second curing agent) that reacts with the reactive group in the structural unit (B) of the meth)acrylic polymer.

Examples of the second curing agent include isocyanate compounds. Examples of isocyanate compounds include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m- or p-phenylene diisocyanate, or a mixture thereof), 4, 4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate, or mixtures thereof) (MDI), 4,4 Aromatic diisocyanates such as '-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or mixtures thereof) (XDI), tetramethyl xylylene isocyanates (1,3- or 1,4-tetramethylxylylene diisocyanate, or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and the like. Isocyanate compounds include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-penta aliphatic diisocyanates such as methylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcapate; ,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate ) (IPDI), methylene bis (cyclohexyl isocyanate) (4,4′-, 2,4′- or 2,2′-methylene bis (cyclohexyl isocyanate), their trans, trans-form, trans, cis-form, cis, cis-form or mixture thereof) (H12MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis Also included are alicyclic diisocyanates such as (isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (H6XDI).

When the first liquid contains the second curing agent, the content of the second curing agent is preferably 0.01% by mass or more based on the total amount of the first liquid and the second liquid, and , preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less.

The first liquid and/or the second liquid may further contain other additives as necessary. Other additives include, for example, curing accelerators, antioxidants, coloring agents, fillers, crystal nucleating agents, heat stabilizers, heat conducting agents, plasticizers, foaming agents, flame retardants, damping agents, flame retardant aids, agents (for example, metal oxides) and the like. Other additives may be used singly or in combination of two or more. The content of other additives may be, for example, 0.1% by mass or more and 30% by mass or less based on the total content of the first liquid and the second liquid.

[Heat storage material]
The cured product of the curable composition described above (including the cured product of the mixture of the first liquid and the second liquid of the curable composition set) is suitably used as a heat storage material (curable composition for heat storage material ). That is, the heat storage material according to one embodiment includes a cured product of the curable composition described above (or a mixture of the first liquid and the second liquid of the curable composition set described above).

A heat storage material can be utilized in various fields. Heat storage materials are used, for example, in automobiles, buildings, public facilities, air conditioning equipment in underground malls (improving the efficiency of air conditioning equipment), piping in factories (heat storage in piping), automobile engines (heat insulation around the engine), electronic parts (Prevention of temperature rise of electronic parts), used for fibers of underwear, etc.

[Article with heat storage material]
Next, a method for obtaining an article provided with a heat storage material will be described by taking an electronic component as an example on which the heat storage material is provided. FIG. 1 is a schematic cross-sectional view showing a method of forming a heat storage material (a method of manufacturing an article provided with a heat storage material) according to one embodiment. In the forming method (manufacturing method) according to the present embodiment, first, as shown in FIG. 1A, an electronic component 1 is prepared as an article on which a heat storage material is provided. The electronic component 1 includes, for example, a substrate (for example, a circuit substrate) 2, a semiconductor chip (heat source) 3 provided on the substrate 2, and a plurality of connection portions (for example, solder) 4 for connecting the semiconductor chip 3 to the substrate 2. It has In this electronic component 1, the semiconductor chip 3 serves as a heat source. A plurality of connection portions 4 are provided between the substrate 2 and the semiconductor chip 3 so as to be spaced apart from each other. That is, a gap exists between the substrate 2 and the semiconductor chip 3 to separate the plurality of connecting portions 4 from each other.

Subsequently, as shown in FIG. 1B, a curable composition 6 is filled between the substrate 2 and the semiconductor chip 3 using, for example, a syringe 5 . The curable composition 6 may be the curable composition according to one embodiment described above or a mixture of the first liquid and the second liquid in the curable composition set according to one embodiment. The curable composition 6 may be completely uncured or partially cured.

When the curable composition 6 is in a liquid state at room temperature (for example, 25° C.), the curable composition 6 can be filled at room temperature. When the curable composition 6 is solid at room temperature, the curable composition 6 can be heated (for example, 50° C. or higher) to be liquefied before filling.

By filling the curable composition 6 as described above, as shown in FIG. 2. It is arranged so as to be in thermal contact with each of the semiconductor chip 3 and the connecting portion 4 .

Subsequently, by curing the curable composition 6, the heat storage material 7 is formed in the gap existing between the substrate 2 and the semiconductor chip 3, as shown in FIG. 1(d).

The method of curing the curable composition 6 may be a method of curing the curable composition 6 by heating the curable composition 6 placed. When a curable composition set is used, the method of curing the curable composition 6 may be a method of advancing curing by mixing the first liquid and the second liquid.

In the above embodiment, the curable composition 6 is in liquid form, but in another embodiment, the curable composition may be in sheet form. FIG. 2 is a schematic cross-sectional view showing another embodiment of the method for forming the heat storage material. In the heat storage material forming method (manufacturing method) of the present embodiment, first, as shown in FIG. 2A, an electronic component 11 is prepared as an article on which the heat storage material is provided. The electronic component 11 includes, for example, a substrate 2 and a semiconductor chip (heat source) 3 provided on the substrate 2 .

Subsequently, as shown in FIG. 2B, a sheet-like curable composition 16 is placed on the substrate 2 and the semiconductor chip 3 so as to be in thermal contact with the substrate 2 and the semiconductor chip 3, respectively. The curable composition 16 is, for example, a composition B-staged (semi-cured) by the above-described curing method. That is, the method for forming the heat storage material of the present embodiment includes a step of B-stageing the first curable composition to prepare the second curable composition (sheet-shaped curable composition 16). good.

Subsequently, by curing the curable composition 16, the heat storage material 17 is formed on the substrate 2 and the semiconductor chip 3 as shown in FIG. 2(c). The curing method of the curable composition 6 may be the same as the curing method described above.

In the above embodiment, the heat storage material is formed so as to cover the entire exposed surface of the heat source, but in another embodiment, the heat storage material may be arranged so as to cover part of the exposed surface of the heat source. . FIG. 3(a) is a schematic cross-sectional view showing another embodiment of an article in which a heat storage material is formed. As shown in FIG. 3A, the heat storage material 17 may be arranged in contact with (covering) part of the exposed surface of the semiconductor chip (heat source) 3, for example. The place where the heat storage material 17 is arranged (the place where the heat storage material 17 contacts the semiconductor chip 3) is the side surface of the semiconductor chip 3 in FIG. good too.

In each of the embodiments described above, the curable compositions 6 and 16 for forming the heat storage materials 7 and 17 are placed in an uncured or semi-cured state so as to be in contact with the semiconductor chip 3 as a heat source. , the curable compositions 6 and 16 are cured. Therefore, the heat storage materials 7 and 17 are formed so as to preferably follow the shape of the semiconductor chip 3 and the like. Therefore, the heat generated by the semiconductor chip 3 which is the heat source and the heat conducted from the semiconductor chip 3 to the substrate 2 are also efficiently conducted to the heat storage materials 7 and 17 and are preferably stored in the heat storage materials 7 and 17 .

In each of the above embodiments, the curable compositions 6 and 16 are arranged so as to be in direct contact with the semiconductor chip 3, which is the heat source, and the heat storage materials 7 and 17 are formed. , It may be in thermal contact with the heat source, and in another embodiment, for example, the curable composition is arranged so as to be in thermal contact with the heat source via a thermally conductive member (heat radiating member, etc.), A heat storage material may be formed.

FIG. 3(b) is a schematic cross-sectional view showing another embodiment of an article in which a heat storage material is formed. As shown in FIG. 3B, the heat storage material 17 is arranged on the surface of the substrate 2 opposite to the surface on which the semiconductor chip 3 is provided. In this embodiment, the heat storage material 17 is not in direct contact with the semiconductor chip 3 , but is in thermal contact with the semiconductor chip 3 via the substrate 2 . The heat storage material 17 may be placed on any surface of the substrate 2 as long as it is in thermal contact with the semiconductor chip 3 . Even in this case, the heat generated by the heat source (semiconductor chip 3 ) is efficiently conducted to the heat storage material 17 through the substrate 2 and is preferably stored in the heat storage material 17 .

In each of the embodiments described with reference to FIGS. 2 and 3, the heat storage material 17 is formed using the B-staged sheet-like curable composition 16 as the curable composition. In an example, the curable composition may be a liquid curable composition. In this case, for example, a liquid curable composition is applied to part or all of the exposed surface of the semiconductor chip (heat source) 3, or the surface of the substrate 2 opposite to the surface on which the semiconductor chip 3 is provided. Then, the heat storage material may be formed by curing.

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

[Synthesis of heat storage (meth)acrylic polymer]
Heat storage (meth)acrylic polymers A and B used in Example 4 were synthesized by a known solution polymerization method as follows.

(Synthesis of heat storage (meth)acrylic polymer A)
A 500 mL flask composed of a stirrer, a thermometer, a nitrogen gas inlet tube, a discharge tube and a heating jacket was used as a reactor, and 93 g of methoxypolyethylene glycol #1000 acrylate and 7 g of glycidyl methacrylate were used as monomers, and 81.8 g of 2-propanol was used as a solvent. Mix, add to reactor, stir at room temperature (25° C.) and flush with nitrogen for 1 hour.
Then, the temperature was raised to 70° C. After completion of the temperature rise, a solution of 0.35 g of azobisisobutyronitrile dissolved in methyl ethyl ketone was added to the reactor to initiate the reaction. After that, the mixture was stirred at an internal temperature of the reactor of 70° C. and reacted for 5 hours. Then, a solution of 0.05 g of azobisisobutyronitrile dissolved in methyl ethyl ketone was added to the reactor, heated to 90° C., and further reacted for 2 hours. Thereafter, the solvent was removed and the polymer was dried to obtain a heat-storage (meth)acrylic polymer A. The heat storage (meth)acrylic polymer A had a weight average molecular weight (Mw) of 15,000.

(Synthesis of heat storage (meth)acrylic polymer B)
The heat-storage (meth)acrylic polymer B was synthesized in the same manner as the synthesis example of the heat-storage (meth)acrylic polymer A, except that glycidyl methacrylate was changed to hydroxyethyl acrylate. The heat-storage (meth)acrylic polymer B thus obtained had a weight average molecular weight (Mw) of 15,000.

[Production of heat storage material]
(Example 1)
In a 50 mL container, 18.1 g of a p-aminophenol type epoxy compound (epoxy compound A) (manufactured by Mitsubishi Chemical Corporation, product name jER630) as an epoxy compound and 3 or 4-methyltetrahydrophthalic anhydride (curing 31.9 g of agent A), 50 g of BA410xxP, C37 (capsule A) (manufactured by Outlast Technology Co., Ltd.) as heat storage capsules, and 0.5 g of 2-ethyl-4-methylimidazole were blended to form a curable composition. Obtained. The viscosity of this curable composition at 50° C. was measured according to JIS Z 8803 using an E-type viscometer (PE-80L manufactured by Toki Sangyo Co., Ltd.). Table 1 shows the results. Next, the curable composition is filled in a 10 cm × 10 cm × 1 mm mold (SUS plate), covered with a SUS plate, and then cured at 120 ° C. for 3 hours under a pressure of 10 kPa to obtain a thickness of 1 mm. A sheet-like heat storage material was obtained.

(Example 2)
In a 50 mL polypropylene container, 25.4 g of ethylene glycol diglycidyl ether (epoxy compound B) (manufactured by Nagase ChemteX Corporation, product name Denacol EX810) as an epoxy compound, and an aqueous dispersion slurry of heat storage capsules (solid content: 40% , Capsules B) (manufactured by Miki Riken Kogyo Co., Ltd., melting point 37° C.) (175 g) were added and stirred and mixed for 2 minutes in a rotation/revolution mixer to prepare a mixed dispersion of the epoxy compound and heat storage capsules. To this mixed dispersion, 4.6 g of diethylenetriamine (curing agent B) was added as a curing agent, mixed with stirring for 1 minute, and defoamed for 30 seconds to prepare a curable composition. The viscosity of this curable composition at 25° C. was measured according to JIS Z 8803 using an E-type viscometer. Table 1 shows the results. Using this curable composition, a molded article was obtained by a gel casting method. Specifically, after the curable composition was cast into a mold, it was solidified in situ by a gelling reaction to obtain a moist cured body. After drying this at 25° C. for 3 days, it was vacuum-dried at 80° C. and a negative pressure of −0.1 MPa to obtain a heat storage material.

(Example 3)
39 g of p-aminophenol type epoxy compound (manufactured by Mitsubishi Chemical Corporation, product name jER630), 1,6-hexanediol diglycidyl ether (1,6-HDDGE, epoxy compound B) (manufactured by Wako Pure Chemical Industries, Ltd.) 9 g and 52 g of BA410xxP, C37 (capsule A) (manufactured by Outlast Technology Co., Ltd.) as heat storage capsules were mixed to obtain a first liquid. As a curing agent, pentaerythritol tetrakis(3-mercaptobutyrate) (curing agent C) 40.5 g, 1,4-bis(3-mercaptobutyryloxy)butane (curing agent D) 6 g, capsule A 51 g, and 2.5 g of dimethylbenzylamine (DMBA) were mixed to obtain a second liquid. The viscosities of the first and second liquids at 25° C. were measured according to JIS Z 8803 using an E-type viscometer (PE-80L manufactured by Toki Sangyo Co., Ltd.). Table 2 shows the results. Next, a 10 cm × 10 cm × 1 mm mold (SUS plate) was placed on the polyethylene terephthalate (PET) film as a spacer, and the first liquid and the second liquid were mixed with a mixing nozzle (manufactured by Tomita Engineering Co., Ltd.). ), covered with another PET film, and cured at room temperature for 24 hours. After curing, the PET film and the formwork were removed to obtain a 1 mm-thick sheet-like cured product (heat storage material).

(Example 4)
The viscosity measurement of the curable composition and the production of the heat storage material were performed in the same manner as in Example 2, except that the composition of the curable composition was changed as shown in Table 2. Table 2 shows the results.

[Performance evaluation of compact]
It was evaluated whether or not the molded article produced from the curable composition was suitably used as a heat storage material. It can be said that the curable composition is suitable for use as a heat storage material when it is excellent in terms of the heat storage capacity shown below. In addition, it can be said that the curable composition is more preferably used as a heat storage material when it is excellent in moldability and suppression of liquid leakage and volatilization as described below.

(Evaluation of melting point and heat storage amount)
Each heat storage material produced in Examples was measured using a differential scanning calorimeter (manufactured by PerkinElmer, model number DSC8500) to calculate the melting point and heat storage amount. Specifically, the temperature was raised to 100°C at a rate of 20°C/min, held at 100°C for 3 minutes, then lowered to -30°C at a rate of 10°C/min, and then held at -30°C for 3 minutes. , and the thermal behavior was measured by heating again to 100° C. at a rate of 10° C./min. The melting peak was taken as the melting point of the heat storage material, and the area was taken as the heat storage amount. Tables 1 and 2 show the results. In addition, if the heat storage amount is 30 J/g or more, it can be said that the heat storage amount is excellent.

(Evaluation of moldability)
A case where a molded article could be produced from the curable composition was rated as A, and B was given when it was not possible. Tables 1 and 2 show the results.

(Evaluation of liquid leakage and volatility)
Weight change was measured before and after the heat storage material was allowed to stand at a temperature of 80° C. in an air atmosphere for 1000 hours, and a weight reduction rate (%) was measured. Tables 1 and 2 show the results.

DESCRIPTION OF SYMBOLS 1, 11... Electronic component, 2... Substrate, 3... Semiconductor chip (heat source), 4... Connection part, 5... Syringe, 6, 16... Curable composition, 7, 17... Heat storage material.

Claims (16)

an epoxy compound;
a capsule having a heat storage component and an outer shell enclosing the heat storage component;
A curable composition containing a curing agent,
The epoxy compound contains at least one selected from the group consisting of a monomer having an epoxy group and a polymer having an epoxy group,
The polymer having an epoxy group includes a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2),
The curable composition , wherein the outer shell of the capsule is made of melamine resin, urethane resin, or silica .

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having an epoxy group. ]

[In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a group having a polyoxyalkylene chain. ] 2. The curable composition according to claim 1 , further comprising a polymer having a structural unit represented by the following formula (3) and having no epoxy group.

[In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain. ] The curable composition according to claim 1 or 2 , wherein the curing agent is at least one selected from the group consisting of phenol compounds, amine compounds, acid anhydrides and imidazole compounds. containing an epoxy compound, a capsule encapsulating a heat storage component, a curing agent, and water,
A curable composition , wherein the epoxy compound is a water-soluble epoxy compound . The curable composition according to claim 4 , wherein the curing agent is at least one selected from the group consisting of thiol compounds and amine compounds. The curable composition according to any one of claims 1 to 5 , which is liquid at 50°C. The curable composition according to any one of claims 1 to 6 , which is used for forming a heat storage material. A heat storage material comprising a cured product of the curable composition according to any one of claims 1 to 7 . A curable composition set comprising a first liquid containing an epoxy compound and a second liquid containing a curing agent,
At least one of the first liquid and the second liquid further contains a capsule having a heat-storage component and an outer shell enclosing the heat-storage component ,
The epoxy compound contains at least one selected from the group consisting of a monomer having an epoxy group and a polymer having an epoxy group,
The polymer having an epoxy group includes a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2),
A curable composition set , wherein the outer shell is made of melamine resin, urethane resin, or silica .

[In the formula, R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having an epoxy group. ]

[In the formula, R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a group having a polyoxyalkylene chain. ] 10. The curable composition according to claim 9 , wherein at least one of the first liquid and the second liquid further contains a polymer having a structural unit represented by the following formula (3) and having no epoxy group. set.

[In the formula, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group having 12 to 30 carbon atoms or a group having a polyoxyalkylene chain. ] The curable composition set according to claim 9 or 10 , wherein the curing agent is at least one selected from the group consisting of thiol compounds and amine compounds. The curable composition set according to any one of claims 9 to 11 , wherein the curing agent is a thiol compound. The curable composition set according to any one of claims 9 to 12 , wherein both said first liquid and said second liquid contain said capsules. The curable composition set according to any one of claims 9 to 13 , which is used for forming a heat storage material. A heat storage material comprising a cured mixture of the first liquid and the second liquid in the curable composition set according to any one of claims 9 to 14 . a heat source;
and the heat storage material according to claim 8 or 15 provided so as to be in thermal contact with the heat source.

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