JPWO2019220662A1 - Curable compositions, curable composition sets, heat storage materials, and articles - Google Patents

Abstract

One aspect of the present invention is a curable composition containing a compound having an isocyanate group and a capsule containing a heat storage component, and the other aspect is a compound having a blocked isocyanate group and a heat storage component. It is a curable composition containing a capsule containing the above and a curing agent.

Description

The present invention relates to curable compositions, curable composition sets, heat storage materials, and articles.

The heat storage material is a material that can take out the stored energy 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 / exterior materials, automobile parts such as canisters, and heat insulating containers.

As a heat storage method, latent heat storage utilizing the phase change of a substance is widely used in terms of the amount of heat. Water-ice is a well-known latent heat storage substance. Water-ice is a substance having a large amount of heat, but its application range is also limited because the phase change temperature is limited to 0 ° C. in the atmosphere. Therefore, paraffin is used as a latent heat storage substance having a phase change temperature higher than 0 ° C. and 100 ° C. or lower. However, paraffin becomes liquid when it undergoes a phase change due to heating, and there is a risk of ignition and ignition. Therefore, in order to use paraffin as a heat storage material, paraffin is stored in a closed container such as a bag. It is necessary to prevent the leakage of paraffin wax, which limits the fields of application.

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

Japanese Unexamined Patent Publication No. 2000-109787

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

［式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はイソシアネート基を有する有機基を表す。］
［５］ イソシアネート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、イソシアネート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。］As a result of diligent research, the present inventors have found that a curable composition or a curable composition set containing a specific component is preferably used as a heat storage material, that is, the curable composition or the curable composition. The present invention was completed by finding that the heat storage material obtained by using the product set has an excellent heat storage amount. The present invention provides the following [1] to [29] in some aspects.
[1] A curable composition containing a compound having an isocyanate group and a capsule containing a heat storage component.
[2] The curable composition according to [1], wherein the compound having an isocyanate group contains a monoma having an isocyanate group.
[3] The curable composition according to [1] or [2], wherein the compound having an isocyanate group contains a polymer having an isocyanate group.
[4] The curable composition according to [3], wherein the polymer having an isocyanate group 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 isocyanate group. ]
[5] The curable composition according to [4], wherein the polymer having an isocyanate group 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 isocyanate 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. ]

［式中、Ｒ^７は水素原子又はメチル基を表し、Ｒ^８はブロックイソシアネート基を有する有機基を表す。］
［１１］ ブロックイソシアネート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、［１０］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。］
［１２］ 下記式（３）で表される構造単位を含み、ブロックイソシアネート基を有さないポリマを更に含有する、［７］〜［１１］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。］
［１３］ 硬化剤が、アルコール化合物、アミン化合物及びチオ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、［７］〜［１２］のいずれかに記載の硬化性組成物。
［１４］ 硬化剤がアルコール化合物である、［７］〜［１２］のいずれかに記載の硬化性組成物。
［１５］ ５０℃において液体状である、［１］〜［１４］のいずれかに記載の硬化性組成物。
［１６］ 蓄熱材の形成に用いられる、［１］〜［１５］のいずれかに記載の硬化性組成物。
［１７］ ［１］〜［１６］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。[7] A curable composition containing a compound having a blocked isocyanate group, a capsule containing a heat storage component, and a curing agent.
[8] The curable composition according to [7], wherein the compound having a blocked isocyanate group contains a monoma having a blocked isocyanate group.
[9] The curable composition according to [7], wherein the compound having a blocked isocyanate group contains a polymer having a blocked isocyanate group.
[10] The curable composition according to [9], wherein the polymer having a blocked isocyanate group contains a structural unit represented by the following formula (4).

[In the formula, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an organic group having a blocked isocyanate group. ]
[11] The curable composition according to [10], wherein the polymer having a blocked isocyanate group 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. ]
[12] The curable composition according to any one of [7] to [11], which contains a structural unit represented by the following formula (3) and further contains a polymer having no blocked isocyanate 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. ]
[13] The curable composition according to any one of [7] to [12], wherein the curing agent is at least one selected from the group consisting of an alcohol compound, an amine compound and a thiol compound.
[14] The curable composition according to any one of [7] to [12], wherein the curing agent is an alcohol compound.
[15] The curable composition according to any one of [1] to [14], which is liquid at 50 ° C.
[16] The curable composition according to any one of [1] to [15], which is used for forming a heat storage material.
[17] A heat storage material containing a cured product of the curable composition according to any one of [1] to [16].

［式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はイソシアネート基を有する有機基を表す。］
［２２］ イソシアネート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、［２１］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。］
［２３］ 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、イソシアネート基を有さないポリマを更に含有する、［１８］〜［２２］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。］
［２４］ 硬化剤が、アルコール化合物、アミン化合物及びチオ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、［１８］〜［２３］のいずれかに記載の硬化性組成物セット。
［２５］ 硬化剤がアルコール化合物である、［１８］〜［２３］のいずれかに記載の硬化性組成物セット。
［２６］ 第一液及び第二液の両方がカプセルを含有する、［１８］〜［２５］のいずれかに記載の硬化性組成物セット。
［２７］ 蓄熱材の形成に用いられる、［１８］〜［２６］のいずれかに記載の硬化性組成物セット。
［２８］ ［１８］〜［２７］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。
［２９］ 熱源と、熱源と熱的に接触するように設けられた、［１７］又は［２８］に記載の蓄熱材と、を備える、物品。[18] A capsule containing a first liquid containing a compound having an isocyanate group and a second liquid containing a curing agent, and at least one of the first liquid and the second liquid contains a heat storage component is further provided. A set of curable compositions to contain.
[19] The curable composition set according to [18], wherein the compound having an isocyanate group contains a monoma having an isocyanate group.
[20] The curable composition set according to [18] or [19], wherein the compound having an isocyanate group contains a polymer having an isocyanate group.
[21] The curable composition set according to [20], wherein the polymer having an isocyanate group 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 isocyanate group. ]
[22] The curable composition set according to [21], wherein the polymer having an isocyanate group 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. ]
[23] Any of [18] to [22], 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 isocyanate group. Crab curable composition 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. ]
[24] The curable composition set according to any one of [18] to [23], wherein the curing agent is at least one selected from the group consisting of an alcohol compound, an amine compound and a thiol compound.
[25] The curable composition set according to any one of [18] to [23], wherein the curing agent is an alcohol compound.
[26] The curable composition set according to any one of [18] to [25], wherein both the first liquid and the second liquid contain capsules.
[27] The curable composition set according to any one of [18] to [26] used for forming a heat storage material.
[28] A heat storage material containing a cured product of a mixture of the first liquid and the second liquid in the curable composition set according to any one of [18] to [27].
[29] An article comprising a heat source and the heat storage material according to [17] or [28], which is 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 that is suitably used for a heat storage material.

It is a schematic cross-sectional view which shows one Embodiment of the formation method of the heat storage material. It is a schematic cross-sectional view which shows the other embodiment of the method of forming a heat storage material. It is a schematic cross-sectional view which shows the other embodiment of the article in which a heat storage material was formed.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate. The present invention is not limited to the following embodiments.

As used herein, the term "(meth) acrylic" means "acrylic" and its corresponding "methacryl".

The weight average molecular weight (Mw) in the present specification means a value determined by using gel permeation chromatography (GPC) under the following conditions and using polystyrene as a standard substance.
-Measuring equipment: HLC-8320GPC (product name, manufactured by Tosoh Corporation)
-Analytical column: TSKgel SuperMultipore HZ-H (3 connected) (Product name, manufactured by Tosoh Corporation)
-Guard column: TSKguardvolume SuperMP (HZ) -H (product name, manufactured by Tosoh Corporation)
-Eluent: THF
・ Measurement temperature: 25 ° C

[Curable composition]
<First Embodiment>
The curable composition according to the first embodiment contains a compound having an isocyanate group and a capsule containing a heat storage component (hereinafter, also referred to as “heat storage capsule”).

The compound having an isocyanate group according to the present embodiment is a compound having at least one isocyanate group in the molecule. A compound having an isocyanate group has a property of being cured at room temperature (for example, 25 ° C.) by reacting the isocyanate group with water. The water may be, for example, the humidity contained in the air. Since the curable composition according to the present embodiment has the above-mentioned properties, it can also be said to be a moisture-curable type or a room temperature-curable type curable composition.

The compound having an isocyanate group may contain a monoma having an isocyanate group.

The monoma having an isocyanate group is preferably a diisocyanate having two isocyanate groups in the molecule. Examples of the diisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylenediisocyanate (m- or p-phenylenediisocyanate, or a mixture thereof), 4,4. '-Diphenyldiisocyanate, 1,5-naphthalenediisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisocyanate, or a mixture thereof) (MDI), 4,4' Aromatic diisocyanates such as −toluidin diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylenediocyanate, 2,3-butylene) Diisocyanate, 1,3-butylenediocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, Aliphatic diisocyanates such as 2,6-diisocyanate methylcapate, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), 3-isosia Natomethyl-3,5,5-trimethylcyclohexylisocyanate (isophorone diisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate, these) trans, trans-form, trans, cis-form, cis, cis-form, or a mixture thereof) (H12MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate), norbornan Alicyclic diisocyanates such as diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (H6XDI) Etc., which have an isocyanate group. The monoma may be these isocyanurate denatured products or burette denatured products.

The compound having an isocyanate group may contain a polymer having an isocyanate group.

式中、Ｒ^１は水素原子又はメチル基を表し、Ｒ^２はイソシアネート基を有する有機基を表す。The polymer having an isocyanate group may be a polymer containing a structural unit represented by the following formula (1) (polymer (A)).

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

When the polymer having an isocyanate group is a polymer (A) containing a structural unit represented by the formula (1), the content of the structural unit represented by the formula (1) is the total structure constituting the polymer (A). It may be 2 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the unit.

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 the structural unit represented by the following formula (2) in addition to the structural unit represented by the formula (1) from the viewpoint of further excellent heat storage property when the heat storage material is formed. 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 to 28, more preferably 12 to 26, is more preferably 12 to 24, particularly preferably 12 to 22. The alkyl group represented by R ^4, for example, dodecyl (lauryl group), a tetradecyl group, a hexadecyl group), an octadecyl group (stearyl group), docosyl (behenyl group), tetracosyl group, hexacosyl group, octacosyl group Can be mentioned. Alkyl group represented by R ⁴ is preferably a dodecyl group (lauryl group), a hexadecyl group, an octadecyl group (stearyl group), and docosyl least one selected from the group consisting of (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 (5), that is, 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, Ra 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. A _{plurality of (CH 2} ) _m existing in the group represented by ^{R 4} may be the same as or different from each other. In other words, a group having a polyoxyalkylene chain represented by R ^4, the polyoxyethylene chain may have only one kind of polyoxypropylene chain and polyoxybutylene chains, have two or more You may.

The ^{alkyl group represented by Ra} may be linear or branched. The ^{number of carbon atoms of the alkyl group represented by Ra} is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. ^Ra is particularly preferably a hydrogen atom or a methyl group.

m is preferably 2 or 3, and 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 excellent heat storage amount of the heat storage material.

When the polymer (A) contains the structural unit represented by the formula (2), the content of the structural unit represented by the formula (2) is 100 parts by mass of all the structural units constituting the polymer (A). It may be preferably 60 parts by mass or more, more preferably 80 parts by mass or more, and for example, 98 parts by mass or less. In that case, the content of the structural unit represented by the above formula (1) may be 2 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of all the structural units constituting the polymer (A). It may be, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 13 parts by mass or less, and particularly preferably 10 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.

The polymer having an isocyanate group may be polyurethane, polyol, polyester or the like having an isocyanate group at the terminal, in addition to the polymer (A) described above.

The above-mentioned compounds having an isocyanate group may be used alone or in combination of two or more. The content of the compound having an isocyanate group 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 capsule from falling off from the cured product of the curable composition. % Or more, more preferably 20% by mass or more, and from the viewpoint of further improving the heat storage property, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 35% by mass or less.

A capsule containing a heat storage component (heat storage capsule) has a heat storage component and an outer shell (shell) containing the heat storage component. The heat storage component may be any component capable of storing heat, and may be, for example, a component having a heat storage property associated with a phase transition. As the heat storage component, a heat storage component having a phase transition temperature suitable for the target temperature is appropriately selected according to the purpose of use. The heat storage component has a solid phase / liquid phase transition point (melting point) showing a solid phase / liquid phase transition at, for example, -30 to 120 ° C. from the viewpoint of obtaining a heat storage effect in a practical range.

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

Specifically, the chain saturated hydrocarbon compound includes n-decane (C10 (number of carbon atoms, the same applies hereinafter), -29 ° C. (transition point (melting point), the same applies hereinafter)), n-undecane (C11, -25). ° C.), n-dodecane (C12, -9 ° C.), n-tridecane (C13, -5 ° C.), n-tetradecane (C14, 6 ° C.), n-pentadecane (C15, 9 ° C.), 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-henicosan (C21) , 41 ° C.), n-docosane (C22, 46 ° C.), n-tricosane (C23, 47 ° C.), n-tetracosane (C24, 50 ° C.), n-pentadecane (C25, 54 ° C.), n-hexakosan (C26). , 56 ° C), n-heptakosan (C27, 60 ° C), n-octadecane (C28, 65 ° C), n-nonakosan (C29, 66 ° C), n-triacontane (C30, 67 ° C), n-tetracontane (C40, 81 ° C.), n-pentacontane (C50, 91 ° C.), n-hexacontane (C60, 98 ° C.), n-hexane (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) containing these heat storage components is preferably formed of a material having a heat resistant temperature sufficiently higher than the transition point (melting point) of the heat storage components. The material forming the outer shell has a heat resistant temperature of, for example, 30 ° C. or higher, preferably 50 ° C. or higher, with respect to the transition point (melting point) of the heat storage component. The heat-resistant temperature is defined as the temperature at which the weight loss of the capsule is measured by 1% when the weight loss of the capsule is measured using a differential thermogravimetric simultaneous measuring device (for example, TG-DTA6300 (manufactured by Hitachi High-Tech Science Co., Ltd.)). Will be done.

As the material for forming the outer shell, a material having strength according to the use of the heat storage material formed by the curable composition is appropriately selected. The outer shell is preferably made of melamine resin, acrylic resin, urethane resin, silica or the like. Examples of capsules having an outer shell made of melamine resin include BA410xxP, 18C, BA410xxP, 37C manufactured by Outlast Technology Co., Ltd., and ThermoMemory FP-16, FP-25, FP-31, and FP manufactured by Mitsubishi Paper Mills Limited. −39, Riken Resin PMCD-15SP, 25SP, 32SP, etc. manufactured by Miki Riken Kogyo Co., Ltd. are exemplified. Examples of capsules having an outer shell made of an acrylic resin (polymethylmethacrylate resin) include Micronal DS5001X and 5040X manufactured by BASF. Examples of capsules having an outer shell made of silica include liken resins LA-15, LA-25, and LA-32 manufactured by Miki Riken Kogyo Co., Ltd.

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, and suppresses damage to the capsule due to a volume change of the heat storage component. From the viewpoint of the above, 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, preferably 100 μm or less, and more preferably 50 μm or less. .. The particle size (average particle size) of the heat storage capsule is measured using a laser diffraction type particle size distribution measuring device (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. The heat storage capacity is measured by differential scanning calorimetry (DSC).

Regarding the method for producing the heat storage capsule, the conventional known production methods such as the interfacial polymerization method, the in-situ polymerization method, the in-liquid curing coating method, and the coacervate method are suitable depending on the heat storage component, the material of the outer shell, and the like. You just have to choose the method.

The content of the heat storage capsule is preferably 40% by mass or more, more preferably 50% by mass or more, 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 capsule is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, from the viewpoint of suppressing the heat storage capsule from falling off from the curable composition.

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。The curable composition is also referred to as a polymer (hereinafter, "heat storage (meth) acrylic polymer") containing a structural unit (structural unit (A)) represented by the following formula (3) from the viewpoint of further enhancing the heat storage effect. ) May be further contained. The polymer containing the structural unit (A) is a polymer having no isocyanate 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 excellent heat storage amount 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% by mass or more, and from the viewpoint of handleability, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less.

The curable composition may further contain other additives, if desired. Other additives include, for example, curing accelerators, antioxidants, colorants, fillers, crystal nucleating agents, heat stabilizers, heat conductive materials, plasticizers, foaming agents, flame retardants, vibration damping agents, dehydrating agents, etc. Examples thereof include flame retardant aids (for example, metal oxides). Other additives may be used alone or in combination of two or more. The content of the 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.

The viscosity of the curable composition at 50 ° C. is preferably 100 Pa · s or less, more preferably 50 Pa · s or less, still more preferably 20 Pa · s or less, and particularly preferably 10 Pa · s, from the viewpoint of excellent fluidity and handleability. It is as follows. 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, and specifically, it was measured by an E-type viscometer (for example, PE-80L manufactured by Toki Sangyo Co., Ltd.). Means a value. The calibration of the viscometer can be performed based on JIS Z 8809-JS14000.

<Second Embodiment>
The curable composition according to the second embodiment contains a compound having a blocked isocyanate group, a capsule containing a heat storage component (heat storage capsule), and a curing agent. The mode of the heat storage capsule is the same as that used for the curable composition according to the first embodiment, and thus the description thereof will be omitted.

式中、Ｂは保護基を表し、＊は結合手を表す。The blocked isocyanate group is an isocyanate group blocked (protected) by a blocking agent (protecting group) that can be desorbed by heat, and is represented by the following formula (6).

In the formula, B represents a protecting group and * represents a bond.

The protecting group in the blocked isocyanate group may be a protecting group that can be desorbed (deprotected) by heating (for example, heating at 80 to 160 ° C.). In the blocked isocyanate group, a substitution reaction between the blocking agent forming the protecting group and the curing agent described later can occur under deprotection conditions (for example, heating conditions of 80 to 160 ° C.). Alternatively, in the blocked isocyanate group, an isocyanate group is generated by deprotection, and the isocyanate group can react with a curing agent described later.

Examples of the blocking agent in the blocked isocyanate group include oxime compounds such as formaldehyde, acetoaldoxime, acetooxime, methylethylketooxime and cyclohexanone oxime; pyrazole compounds such as pyrazole, 3-methylpyrazole and 3,5-dimethylpyrazole; ε- Lactam compounds such as caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam; mercaptan compounds such as thiophenol, methylthiophenol and ethylthiophenol; acid amide compounds such as acetate and benzamide; Examples thereof include imide compounds such as acid imide. The blocking agent is preferably a pyrazole compound.

The compound having a blocked isocyanate group may contain a monoma having a blocked isocyanate group.

The monoma having a blocked isocyanate group is preferably a compound in which the isocyanate group is protected by the above-mentioned blocking agent in the monoma having an isocyanate group in the first embodiment.

The compound having a blocked isocyanate group may contain a polymer having a blocked isocyanate group.

式中、Ｒ^７は水素原子又はメチル基を表し、Ｒ^８はブロックイソシアネート基を有する有機基を表す。ブロックイソシアネート基は、上述した式（６）で表される基である。The polymer having a blocked isocyanate group is preferably a compound in which the isocyanate group is protected by the above-mentioned blocking agent in the polymer having an isocyanate group in the first embodiment. That is, the polymer having a blocked isocyanate group is, in one embodiment, a polymer (polymer (B)) containing a structural unit represented by the following formula (4).

In the formula, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an organic group having a blocked isocyanate group. The blocked isocyanate group is a group represented by the above-mentioned formula (6).

When the polymer having a blocked isocyanate group is a polymer (B) containing a structural unit represented by the formula (4), the content of the structural unit represented by the formula (4) is the total mass constituting the polymer (A). It may be 2 parts by mass or more and 95 parts by mass or less with respect to 100 parts by mass of the structural unit.

The polymer (B) further contains the structural unit represented by the above formula (2) in addition to the structural unit represented by the formula (4) from the viewpoint of further excellent heat storage property when the heat storage material is formed. You can go out. Since the structural unit represented by the formula (2) is the same as the embodiment in the first embodiment described above, the description thereof will be omitted.

The weight average molecular weight of the polymer (B) 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.

The content of the compound having a blocked isocyanate 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 capsule from falling off from the cured product of the curable composition. % Or more, more preferably 20% by mass or more, and from the viewpoint of further improving the heat storage property, it is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 35% by mass or less.

The curing agent is preferably at least one selected from the group consisting of alcohol compounds, amine compounds and thiol compounds. The curing agent is more preferably an alcohol compound.

Examples of the alcohol compound include trifunctional or higher functional polyhydric alcohols or monomeric glycols, glycols, and high molecular weight polyols other than these.

Examples of the trifunctional or higher functional polyhydric alcohol or monomeric glycol include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, erythritol, sorbitol, pentaerythritol, and the like. Dipentaerythritol and the like can be mentioned.

Examples of the glycol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-. Methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propane Diol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, neo Pentyl glycol, 1,3,5-trimethyl-1,3-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl Aliphatic glycols such as -1,8-octanediol, alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol, aromatics such as xylylene glycol and bishydroxyethoxybenzene. Glycol and the like can be mentioned.

Examples of the high molecular weight polyol include glycols, polyether polyols, polyester polyols, polyether ester polyols, polycarbonate polyols, and polyacrylic polyols, which are additives of bisphenol A and ethylene oxide or propylene oxide.

The polyether polyol is a hydroxyl group-containing polyether polyol obtained by addition-polymerizing the above-mentioned trifunctional or higher functional alcohol, glycol, or polyamine compound such as ethylenediamine or toluenediamine with an alkylene oxide such as ethylene oxide or propylene oxide. It may be a polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

Polyester polyols include dicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, etc.) or tri or tetracarboxylic acids (trimellitic acid, pyromellitic acid, etc.) and diols (ethylene glycol, propylene glycol, etc.). , 1,4-Butanediol, 1,5-pentanediol, 3-methyl-1,5 pentanediol, 2,2-diethylpropanediol, 2-ethyl-2-putylpropanediol, 1,6-hexanediol , Neopentyl glycol, diethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, etc.), triol (trimethylolpropane, glycerin, etc.) or bisphenol (bisphenol A, bisphenol F, etc.) It may be obtained by a polycondensation reaction.

The polyether ester polyol may be obtained by reacting a mixture with an ether group-containing diol or other glycol with the above-mentioned dicarboxylic acid or an anhydride thereof. Alternatively, it may be obtained by reacting polyester glycol with alkylene oxide (poly (polytetramethylene ether) adipate or the like).

Polycarbonate polyols are a dealcohol condensation reaction between a polyhydric alcohol and a dialkyl carbonate (dimethyl carbonate, diethyl carbonate, etc.), a dephenol condensation reaction between a polyhydric alcohol and a diphenyl carbonate, and a deethylene glycol condensation reaction between a polyhydric alcohol and an ethylene carbonate. It may be obtained by a reaction or the like. Examples of the polyhydric alcohol in this case include 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2, With aliphatic diols such as 2-diethylpropanediol, 2-ethyl2-butylpropanediol and neopentyl glycol, or alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol. It may be there.

Examples of the amine compound include aliphatic amines such as diethylenetriamine, hexamethylenediamine and triethylenetetramine, aromatic amines such as xylenediamine, and alicyclic amines such as isophoronediamine. In the present specification, the amine compound may be an amino alcohol such as monoethanolamine or diethanolamine.

Examples of the thiol compound include pentaerythritol tetrakis (3-mercaptobutyrate) (for example, "Carens MT-PE1" (manufactured by Showa Denko KK)), 1,3,5-tris (3-mercaptobutylyloxy). Ethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trion (for example, "Carens MT-NR1" (manufactured by Showa Denko KK)) and the like can be mentioned.

The content of the curing agent is preferably 0.01% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, based on the total amount of the curable composition. Is.

The curable composition according to the present embodiment also further contains a polymer (heat storage (meth) acrylic polymer) containing the structural unit (A) represented by the above formula (3) from the viewpoint of further enhancing the heat storage effect. You may. Since the aspect of the structural unit (A) is the same as that described above, the description thereof will be omitted.

The curable composition may further contain other additives, if desired. The other additives may be the same additives as those used in the curable composition according to the first embodiment.

The curable composition according to this embodiment may be in a liquid state at 50 ° C. The viscosity of the curable composition at 50 ° C. may be the same as that of the curable composition according to the first embodiment.

[Curable composition set]
The curable composition set according to one embodiment comprises a first liquid containing the above-mentioned compound having an isocyanate group and a second liquid containing a curing agent, and at least one of the first liquid and the second liquid. However, it further contains a capsule containing a heat storage component (heat storage capsule). The embodiments of the compound having an isocyanate group and the heat storage capsule are the same as those used in the curable composition according to the first embodiment, and thus the description thereof will be omitted.

That is, in the curable composition set, the first liquid may contain a compound having an isocyanate group, and may contain a compound having an isocyanate group and a heat storage capsule. The second liquid may contain a curing agent, and may contain a curing agent and a heat storage capsule. The curable composition set preferably comprises a first solution containing a compound having an isocyanate group and a heat storage capsule, and a second solution containing a curing agent and a heat storage capsule.

By mixing the first liquid and the second liquid, the compound having an isocyanate group reacts with the curing agent to obtain a cured product of a 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 a mixture of the first liquid and the second liquid (curable composition) can be immediately obtained. .. That is, in the curable composition set according to the present embodiment, the mixture containing the compound having an isocyanate group can be cured at a high speed.

The content of the compound having an isocyanate group is preferably 2% by mass or more based on the total amount of the first liquid and the second liquid from the viewpoint of suppressing the heat storage capsule from falling off from the cured product of the curable composition. , More preferably 5% by mass or more, further preferably 7% by mass or more, particularly preferably 10% by mass or more, and from the viewpoint of further improving the heat storage property, preferably 50% by mass or less, more preferably 30% by mass or less. It is more preferably 25% by mass or less, and particularly preferably 20% by mass or less.

The content of the heat storage capsule (the total content of the heat storage capsule 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 reference, it is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. The content of the heat storage capsule is preferably 90% by mass or less, based on the total amount of the first liquid and the second liquid, from the viewpoint of suppressing the heat storage capsule from falling off from the cured product of the curable composition. It is preferably 85% by mass or less, more preferably 80% by mass or less.

The curing agent contained in the second liquid is preferably at least one selected from the group consisting of alcohol compounds, amine compounds and thiol compounds. The curing agent is more preferably an alcohol compound. A more specific embodiment of the curing agent may be the same as that of the curing agent used in the second embodiment described above.

The content of the curing agent is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, particularly preferably 10% by mass or more, and preferably 10% by mass or more, based on the total amount of the second liquid. Is 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, and particularly preferably 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 above formula (3). You may. Since the aspect of the structural unit (A) is the same as that described above, the description thereof will be omitted.

When at least one of the first liquid and the second liquid contains a heat storage (meth) acrylic polymer, the heat storage (meth) acrylic polymer further contains a structural unit (structural unit (B)) having a reactive group. You may.

The structural unit (B) has a reactive group. When the first liquid contains a heat-storing (meth) acrylic polymer having a structural unit (B), the reactive group in the structural unit (B) may be a group capable of reacting with the above-mentioned curing agent, for example. It may be an epoxy group, preferably a glycidyl group.

式中、Ｒ^９は水素原子又はメチル基を表し、Ｒ^１０は水素原子又は反応性基を有する有機基を表す。Ｒ^１０における反応性基はエポキシ基を有する基であってよく、好ましくはグリシジル基である。When the first liquid contains a heat storage (meth) acrylic polymer having a structural unit (B), the structural unit (B) is preferably a structural unit represented by the following formula (7).

In the formula, R ⁹ represents a hydrogen atom or a methyl group, and R ¹⁰ represents an organic group having a hydrogen atom or a reactive group. The reactive group in R ¹⁰ may be a group having an epoxy group, preferably a glycidyl group.

When the second liquid contains a heat storage (meth) acrylic polymer having a structural unit (B), the reactive group in the structural unit (B) is selected from, for example, the group consisting of a carboxyl group, a hydroxyl group and an amino group. At least one group.

式中、Ｒ^１１は水素原子又はメチル基を表し、Ｒ^１２は水素原子又は反応性基を有する有機基を表す。Ｒ^１２における反応性基は、カルボキシル基、ヒドロキシル基、又はアミノ基であってよい。When the second liquid contains a heat storage (meth) acrylic polymer having a structural unit (B), the structural unit (B) is preferably a structural unit represented by the following formula (8).

In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents an organic group having a hydrogen atom or a reactive group. The reactive group in R ¹² may be a carboxyl group, a hydroxyl group, or an amino group.

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 thereof (heat storage (meth) acrylic contained in the first liquid and the second liquid). The total content of the polymer) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30 based on the total amount of the first liquid and the second liquid from the viewpoint of further enhancing the heat storage effect. It is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less from the viewpoint of handleability.

When the first liquid contains a heat storage (meth) acrylic polymer containing a structural unit (B), the second liquid is cured as described above from the viewpoint of suppressing liquid leakage and volatilization of the heat storage material and improving heat resistance. In addition to the agent (first curing agent), a curing agent (second curing agent) that reacts with the reactive group in the structural unit (B) of the heat storage (meth) acrylic polymer may be contained.

The second curing agent may be, for example, a phenol compound, an amine compound, an imidazole compound, or an acid anhydride. The amine compound used as the second curing agent may be an amine compound (second amine compound) different from the amine compound (first amine compound) in the first curing agent described above.

Examples of the phenol compound include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, and 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 compound having a diisopropyridene skeleton; phenolic compound having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; cresol compound; ethylphenol compound; butylphenol compound; octylphenol compound; bisphenol A, Novolac resin made from various phenols such as bisphenol F, bisphenol S, and naphthol compound, xylylene skeleton-containing phenol novolac resin, dicyclopentadiene skeleton-containing phenol novolac resin, biphenyl skeleton-containing phenol novolac resin, fluorene skeleton-containing phenol novolac resin, furan Examples thereof include various novolak resins such as skeleton-containing phenol novolak resins.

Examples of the amine compound (second amine compound) include diaminodiphenylmethane, diaminodiphenylsulphon, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, and m-xylylenedi. Aromatic amines such as amines, ethylenediamine, diethylenediamine, hexamethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, aliphatic amines such as polyetherdiamine; dicyandiamide, 1- (o-tolyl) ) Examples thereof include guanidine compounds such as biguanide.

Examples of the imidazole compound include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole and 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 isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-dihydroxymethylimidazole, 2 Examples thereof include −phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like.

Examples of the acid anhydride include aromatics such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol trimellitic anhydride, and biphenyltetracarboxylic acid anhydride. Carboxic acid anhydride; anhydrides of aliphatic carboxylic acids such as azelaic acid, sebacic acid, dodecanedic acid, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, nagic acid anhydride, het acid anhydride, hymic acid anhydride Examples thereof include alicyclic carboxylic acid anhydrides and the like.

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

The first liquid and / or the second liquid may further contain other additives, if necessary. Other additives include, for example, curing accelerators, antioxidants, colorants, fillers, crystal nucleating agents, heat stabilizers, heat conductive materials, plasticizers, foaming agents, flame retardants, vibration damping agents, dehydrating agents, etc. Examples thereof include flame retardant aids (for example, metal oxides). Other additives may be used alone or in combination of two or more. The content of the 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 first liquid and the second liquid.

[Heat storage material]
The cured product of the curable composition described above and the cured product of the mixture of the first liquid and the second liquid of the curable composition set are suitably used as a heat storage material (suitable as a curable composition for a heat storage material). is there). That is, the heat storage material according to one embodiment contains the cured product of the above-mentioned curable composition. Further, the heat storage material according to another embodiment contains a cured product of a mixture of the first liquid and the second liquid of the above-mentioned curable composition set.

The heat storage material can be used in various fields. Heat storage materials include, for example, air conditioning equipment (improving the efficiency of air conditioning equipment) in automobiles, buildings, public facilities, underground streets, etc., piping in factories (heat storage of piping), automobile engines (heat retention around the engine), electronic parts. (Prevents temperature rise of electronic parts), used for underwear fibers, etc.

[Articles with heat storage material]
Next, a method of obtaining an article provided with the heat storage material will be described by taking an electronic component as an example of providing the heat storage material. 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 an embodiment. In the forming method (manufacturing method) according to the present embodiment, first, as shown in FIG. 1A, the electronic component 1 is prepared as an article to which the heat storage material is provided. The electronic component 1 includes, for example, a substrate (for example, a circuit board) 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 the electronic component 1, the semiconductor chip 3 serves as a heat source. The plurality of connecting portions 4 are provided between the substrate 2 and the semiconductor chip 3 so as to be separated from each other. That is, there is a gap between the substrate 2 and the semiconductor chip 3 that separates the plurality of connecting portions 4.

Subsequently, as shown in FIG. 1B, for example, a syringe 5 is used to fill the curable composition 6 between the substrate 2 and the semiconductor chip 3. 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 in a completely uncured state, or may be in a partially cured state.

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 in a solid state at room temperature, the curable composition 6 can be heated (for example, 50 ° C. or higher) to make it liquid and then filled.

By filling the curable composition 6 as described above, as shown in FIG. 1 (c), the curable composition 6 fills the above-mentioned gap existing between the substrate 2 and the semiconductor chip 3 with the substrate. 2. 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, as shown in FIG. 1D, the heat storage material 7 is formed in the above-mentioned gap existing between the substrate 2 and the semiconductor chip 3.

In the curing method of the curable composition 6, when the curable composition according to the first embodiment is used, the arranged curable composition is allowed to stand and then reacted with water in the air to be cured. It may be a method of making it. The curing method of the curable composition 6 is a method of curing the curable composition 6 by heating the arranged curable composition 6 when the curable composition according to the second embodiment is used. It may be there. When the curable composition set is used, the curing method of the curable composition 6 may be a method of advancing the curing by mixing the first liquid and the second liquid.

In the above embodiment, the curable composition 6 is in the form of a liquid, but in another embodiment, the curable composition may be in the form of a sheet. FIG. 2 is a schematic cross-sectional view showing another embodiment of the method for forming the heat storage material. In the method for forming the heat storage material (manufacturing method) of the present embodiment, first, as shown in FIG. 2A, the electronic component 11 is prepared as an article to 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, the sheet-shaped curable composition 16 is arranged on the substrate 2 and the semiconductor chip 3 so as to be in thermal contact with each of the substrate 2 and the semiconductor chip 3. The curable composition 16 is, for example, a composition that has been B-staged (semi-cured) by the above-mentioned curing method. That is, the method for forming the heat storage material of the present embodiment includes a step of B-stage 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. 2C. 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 a part of the exposed surface of the heat source. .. FIG. 3A is a schematic cross-sectional view showing another embodiment of the article on which the heat storage material is formed. As shown in FIG. 3A, the heat storage material 17 may be arranged in contact with (covering a part of) a 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 a side surface portion of the semiconductor chip 3 in FIG. 3A, but is on any surface of the semiconductor chip 3. May be good.

In each of the above-described embodiments, the curable compositions 6 and 16 for forming the heat storage materials 7 and 17 are arranged in an uncured or semi-cured state so as to be in contact with the semiconductor chip 3 which is a heat source. , 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 a heat source and the heat conducted from the semiconductor chip 3 to the substrate 2 are efficiently conducted to the heat storage materials 7 and 17, and are suitably 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 a heat source, and the heat storage materials 7 and 17 are formed. , It suffices to 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 heat conductive member (heat radiating member or the like). A heat storage material may be formed.

FIG. 3B is a schematic cross-sectional view showing another embodiment of the article on which the 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 the present 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 location where the heat storage material 17 is arranged may be 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 via the substrate 2 and is suitably stored in the heat storage material 17.

In each of the embodiments described with reference to FIGS. 2 to 3, the heat storage material 17 is formed by using the B-staged sheet-like curable composition 16 as the curable composition, but the modification of each embodiment In the example, the curable composition may be a liquid curable composition. In this case, for example, a liquid curable composition is applied to a 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. A heat storage material may be formed by curing the heat storage material.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

[Synthesis of heat storage (meth) acrylic polymer]
As described below, the heat storage (meth) acrylic polymers A and B used in Examples 3 to 4 were synthesized by a known solution polymerization method.

(Synthesis of heat storage (meth) acrylic polymer A)
A 500 mL flask composed of a stirrer, a thermometer, a nitrogen gas introduction 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 2-isocyanatoethyl methacrylate (MOI) as monomas were used as a solvent. 81.8 g of 2-propanol was mixed, added to the reactor, stirred at room temperature (25 ° C.), and nitrogen was allowed to flow for 1 hour.
Then, the temperature was raised to 70 ° C., and after the temperature rise was completed, a solution prepared by dissolving 0.35 g of azobisisobutyronitrile in methyl ethyl ketone was added to the reactor to start the reaction. Then, the mixture was stirred at a reactor internal temperature of 70 ° C. and reacted for 5 hours. Then, a solution prepared by dissolving 0.05 g of azobisisobutyronitrile in methyl ethyl ketone was added to the reactor, the temperature was raised to 90 ° C., and the reaction was further carried out for 2 hours. Then, the solvent was removed and dried to obtain a heat storage (meth) acrylic polymer A. The weight average molecular weight (Mw) of the heat storage (meth) acrylic polymer A was 15,000.

(Synthesis of heat storage (meth) acrylic polymer B)
The heat storage (meth) acrylic polymer B was synthesized by the same method as in the synthesis example of the heat storage (meth) acrylic polymer A, except that the MOI was changed to hydroxyethyl acrylate. The weight average molecular weight (Mw) of the obtained heat storage (meth) acrylic polymer B was 15,000.

[Making heat storage material]
(Example 1)
Hexamethylene diisocyanate (HDI) 40 g, BA410xxP, C37 (capsule A) (manufactured by Outlast Technology) 60 g, and dibutyltin dilaurate 0.2 g were blended as heat storage capsules to obtain a curable composition. The viscosity of this curable composition at 50 ° C. was measured using an E-type viscometer (PE-80L, manufactured by Toki Sangyo Co., Ltd.) based on JIS Z 8803. The results are shown in Table 1. Next, the curable composition was applied onto a polyethylene terephthalate (PET) film and cured at room temperature for 24 hours. Then, the PET film was removed to obtain a film-like heat storage material having a thickness of 100 μm.

(Example 2)
83 g of MF-K60B (solid content 60%, manufactured by Asahi Kasei Corporation), which is a compound having a blocked isocyanate group, and 50 g of BA410xxP, C37 were mixed to remove the solvent. Then, 2.0 g of diethylenetriamine and 0.25 g of dibutyltin dilaurate were further mixed to obtain a curable composition. The viscosity of this curable composition at 50 ° C. was measured using an E-type viscometer (PE-80L, manufactured by Toki Sangyo Co., Ltd.) based on JIS Z 8803. The results are shown in Table 1.
Next, the curable composition was filled in a 10 cm × 10 cm × 1 mm mold (SUS plate) and cured at 150 ° C. for 5 minutes to obtain a sheet-shaped heat storage material having a thickness of 1 mm.

(Example 3)
45 g of A201H (manufactured by Asahi Kasei Corporation), which is a compound having an isocyanate group, and 55 g of BA410xxP, C37 were mixed to obtain a first liquid. Further, 45 g of the polyol GP1000 (curing agent) (manufactured by Sanyo Chemical Industries, Ltd.), 55 g of BA410xxP, C37, and 0.16 g of dibutyltin dilaurate were mixed to obtain a second liquid. The viscosities of the first liquid and the second liquid at 25 ° C. were measured using an E-type viscometer (PE-80L manufactured by Toki Sangyo Co., Ltd.) based on JIS Z 8803. The results are shown in Table 2. Next, a 10 cm × 10 cm × 1 mm mold (SUS plate) was installed as a spacer on the polyethylene terephthalate (PET) film, and the first liquid and the second liquid were mixed therein by a mixing nozzle (manufactured by Tomita Engineering Co., Ltd.). ) Was mixed and filled, covered with another PET film, and cured at room temperature for 24 hours. After curing, the PET film and the mold were removed to obtain a sheet-shaped heat storage material having a thickness of 1 mm.

(Example 4)
The viscosity of the curable composition was measured and the heat storage material was prepared in the same manner as in Example 3 except that the composition of the curable composition was changed as shown in Table 2. The results are shown in Table 2.

[Evaluation of melting point and heat storage]
Each heat storage material produced in the examples was measured using a differential scanning calorimetry meter (manufactured by PerkinElmer, model number DSC8500), and the melting point and heat storage amount were calculated. Specifically, the temperature is raised to 100 ° C. at 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. The temperature was raised again to 100 ° C. at a rate of 10 ° C./min and the thermal behavior was measured. The melting peak was defined as the melting point of the heat storage material, and the area was defined as the amount of heat storage. The results are shown in Tables 1 and 2. If the heat storage amount is 30 J / g or more, it can be said that the heat storage amount is excellent.

1,11 ... Electronic components, 2 ... Substrates, 3 ... Semiconductor chips (heat source), 4 ... Connections, 5 ... Syringes, 6,16 ... Curable compositions, 7, 17 ... Heat storage materials.

Claims (29)

A curable composition containing a compound having an isocyanate group and a capsule containing a heat storage component. The curable composition according to claim 1, wherein the compound having an isocyanate group contains a monoma having an isocyanate group. The curable composition according to claim 1 or 2, wherein the compound having an isocyanate group contains a polymer having an isocyanate group. The curable composition according to claim 3, wherein the polymer having an isocyanate group 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 isocyanate group. ] The curable composition according to claim 4, wherein the polymer having an isocyanate group 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. ] The curable composition according to any one of claims 1 to 5, further comprising a polymer having a structural unit represented by the following formula (3) and having no isocyanate 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. ] A curable composition containing a compound having a blocked isocyanate group, a capsule containing a heat storage component, and a curing agent. The curable composition according to claim 7, wherein the compound having a blocked isocyanate group contains a monoma having a blocked isocyanate group. The curable composition according to claim 7, wherein the compound having a blocked isocyanate group contains a polymer having a blocked isocyanate group. The curable composition according to claim 9, wherein the polymer having a blocked isocyanate group contains a structural unit represented by the following formula (4).

[In the formula, R ⁷ represents a hydrogen atom or a methyl group, and R ⁸ represents an organic group having a blocked isocyanate group. ] The curable composition according to claim 10, wherein the polymer having a blocked isocyanate group 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. ] The curable composition according to any one of claims 7 to 11, further containing a polymer having a structural unit represented by the following formula (3) and having no blocked isocyanate 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 any one of claims 7 to 12, wherein the curing agent is at least one selected from the group consisting of an alcohol compound, an amine compound and a thiol compound. The curable composition according to any one of claims 7 to 12, wherein the curing agent is an alcohol compound. The curable composition according to any one of claims 1 to 14, which is liquid at 50 ° C. The curable composition according to any one of claims 1 to 15, which is used for forming a heat storage material. A heat storage material containing a cured product of the curable composition according to any one of claims 1 to 16. A first liquid containing a compound having an isocyanate group and a second liquid containing a curing agent are provided.
A curable composition set in which at least one of the first liquid and the second liquid further contains a capsule containing a heat storage component. The curable composition set according to claim 18, wherein the compound having an isocyanate group contains a monoma having an isocyanate group. The curable composition set according to claim 18 or 19, wherein the compound having an isocyanate group contains a polymer having an isocyanate group. The curable composition set according to claim 20, wherein the polymer having an isocyanate group 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 isocyanate group. ] The curable composition set according to claim 21, wherein the polymer having an isocyanate group 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. ] Any one of claims 18 to 22, wherein at least one of the first liquid and the second liquid further contains a polymer represented by the following formula (3) and does not have an isocyanate group. The curable composition set according to.

[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 any one of claims 18 to 23, wherein the curing agent is at least one selected from the group consisting of an alcohol compound, an amine compound and a thiol compound. The curable composition set according to any one of claims 18 to 23, wherein the curing agent is an alcohol compound. The curable composition set according to any one of claims 18 to 25, wherein both the first liquid and the second liquid contain the capsule. The curable composition set according to any one of claims 18 to 26, which is used for forming a heat storage material. A heat storage material comprising a cured product of a mixture of the first liquid and the second liquid in the curable composition set according to any one of claims 18 to 27. With a heat source
An article comprising the heat storage material according to claim 17 or 28, which is provided so as to be in thermal contact with the heat source.

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