JPWO2019221134A1 - Heat storage moldings, curable compositions and articles - Google Patents

Abstract

One aspect of the present invention is a heat storage molded product containing a resin and microcapsules dispersed in the resin and containing a heat storage component, and the resin contains a cured product of a water-soluble epoxy compound.

Description

The present disclosure relates to heat storage molded articles, curable compositions 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 for energy saving, exhaust heat utilization, suppression of rapid temperature rise and fall, etc., for air conditioning equipment, floor heating equipment, refrigerators, automobile interior / exterior materials, electronic parts such as IC chips, automobile parts such as canisters, etc. It is used for applications such as heat insulation 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. As the latent heat storage, the one utilizing the phase change of water-ice is well known. The phase change of water-ice is advantageous in terms of the amount of heat, but the range of application is also limited because the phase change temperature is limited to 0 ° C. in the atmosphere. Therefore, hydrocarbons are used as latent heat storage materials having a phase change temperature of -30 to 120 ° C.

However, in order to use a hydrocarbon that becomes liquid due to a phase change as a heat storage material, it is necessary to enclose the hydrocarbon in a highly airtight container or film. On the other hand, when the heat storage material is sealed in a container, the applicable place of the heat storage material is remarkably limited. Therefore, at present, heat storage microcapsules in which a latent heat storage material is sealed in an outer shell (shell) formed of a melamine resin or the like are used.

The heat storage microcapsules are used by being dispersed in a material such as a resin. When using heat storage microcapsules, it is necessary to increase the heat storage density by increasing the filling density of the heat storage microcapsules in the resin in order to maintain energy saving, heat absorption / heat dissipation for a long time, and the like. For example, Patent Document 1 discloses a heat storage sheet having a heat ^{storage density of 70 J / cm 3} or more by heat-pressing a fiber structure in which heat storage microcapsules are supported.

Further, the heat storage material containing the heat storage microcapsules may be molded into a sheet shape by, for example, pouring it into a molding mold. In such a case, it is required that the heat storage microcapsules are not damaged during molding and the heat storage material does not leak. For example, Patent Document 2 discloses a heat storage sheet using a solcast film of a vinyl sol coating liquid containing vinyl chloride resin particles and a heat storage material.

Japanese Unexamined Patent Publication No. 2016-1420556 International Publication No. 2015/098739

As described in Patent Document 1, in order to improve the heat storage density, it is desirable to add, for example, 60% by mass or more of heat storage microcapsules. On the other hand, since the molded product has high rigidity and inferior moldability in proportion to the amount of addition, it is described in Patent Document 2 from the viewpoint of ensuring moldability while preventing damage to the heat storage microcapsules. In addition, it is necessary to reduce the amount of heat storage microcapsules added to, for example, about 30% by mass. That is, a large amount of heat storage and excellent moldability are in a trade-off relationship with each other, and it is not easy to realize a heat storage molded product that satisfies both at the same time.

Therefore, one aspect of the present invention is to provide a heat storage molded product having an excellent heat storage amount and moldability.

By using a water-soluble epoxy compound together with the heat storage microcapsules, the present inventors can mold the heat storage molded body in a state where the heat storage microcapsules are dispersed in water, and therefore, the content of the heat storage microcapsules. It was found that formability can be ensured even if the amount of heat is increased, and as a result, a large amount of heat storage can be obtained.

One aspect of the present invention is a heat storage molded product containing a resin and microcapsules dispersed in the resin and containing a heat storage component, and the resin contains a cured product of a water-soluble epoxy compound. This heat storage molded body is excellent in heat storage amount and moldability.

Another aspect of the present invention is a curable composition containing a water-soluble epoxy compound and microcapsules containing a heat storage component. By using this cured composition, the above-mentioned heat storage molded product having excellent heat storage amount and moldability can be preferably obtained.

式（１）中、ｎは１〜２２の整数を表す。In each of the above aspects, the water-soluble epoxy compound may be a glycidyl ether compound, preferably a compound represented by the following formula (1).

In equation (1), n represents an integer of 1 to 22.

Since the heat storage molded body may be used by being attached to a curved surface, for example, it is desirable that the heat storage molded body has flexibility so that it can be deformed according to the shape to be applied (for example, a curved surface). When the epoxy compound is a compound represented by the formula (1), a heat storage molded body having excellent flexibility in addition to the amount of heat storage and moldability can be obtained.

In the heat storage molded product, the content of the microcapsules may be 10 to 80% by mass based on the total amount of the heat storage molded product, the particle size of the microcapsules may be 0.2 to 100 μm, and the resin content. The amount may be 10 to 80% by mass based on the total amount of the heat storage molded product. The heat storage molded product may have a heat storage capacity of 100 J / g or more.

The curable composition may further contain a curing agent and may further contain water.

The heat storage molded product may contain a cured product of the above curable composition.

Another aspect of the present invention is an article comprising a heat source and the heat storage molded body 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 heat storage molded product having an excellent heat storage amount and moldability.

It is sectional drawing which shows one Embodiment of the heat storage molded body. It is a schematic cross-sectional view which shows one Embodiment of an article and its manufacturing method. FIG. 5 is a schematic cross-sectional view showing another embodiment of the article.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings as appropriate.

FIG. 1 is a cross-sectional view showing an embodiment of a heat storage molded product. As shown in FIG. 1, the heat storage molded product 1 according to the embodiment includes a resin 2 and microcapsules (hereinafter, also simply referred to as “microcapsules” or “heat storage microcapsules”) 3 containing a heat storage component. Contains. The microcapsules 3 are dispersed in the resin 2 in the state of primary particles or agglomeration. The heat storage molded body 1 is molded into, for example, a sheet. The thickness of the sheet-shaped heat storage molded body 1 may be, for example, 0.1 mm or more and 5 mm or less.

The resin 2 constitutes the matrix of the heat storage molded body 1. The content of the resin is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 50% by mass or more, preferably 80% by mass or less, and 10% by mass or less, based on the total amount of the heat storage molded product. It may be -80% by mass, 30-80% by mass, or 50-80% by mass.

Resin 2 is a cured product of a water-soluble epoxy compound. The water-soluble epoxy compound is a compound having an epoxy group and dissolving 1 g or more in 100 g of water. It can be visually confirmed that the water-soluble epoxy compound is dissolved in water. The water-soluble epoxy compound may be liquid, for example, at room temperature (25 ° C.).

The water-soluble epoxy compound may be, for example, a glycidyl ether compound. The glycidyl ether compound may be, for example, a compound in which hydrogen atoms in some or all of the hydroxyl groups of the 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 the water-soluble epoxy compound (glycidyl ether compound) as described above include glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene. Glycoldiglycidyl ether and the like can be mentioned. These water-soluble epoxy compounds may be used alone or in combination of two or more.

The polyhydric alcohol constituting the water-soluble epoxy compound (glycidyl ether compound) may be linear or branched, and is preferably linear from the viewpoint of excellent flexibility. From the same viewpoint, the content of the water-soluble epoxy compound (glycidyl ether compound) composed of the linear polyhydric alcohol is preferably 10% by mass or more, more preferably 20 based on the total amount of the water-soluble epoxy compound. It is mass% or more, more preferably 30 mass% or more.

The content of the water-soluble epoxy compound is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, and preferably 80% by mass or less, based on the total amount of the heat storage molded body. More preferably 60% by mass or less, further preferably 40% by mass or less, 10 to 80% by mass, 30 to 80% by mass, 50 to 80% by mass, 10 to 60% by mass, 30 to 60% by mass, 50 to 50 to It may be 60% by mass, 10 to 40% by mass, or 30 to 40% by mass.

式（１）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。From the viewpoint of excellent flexibility of the heat storage molded body 1, the water-soluble epoxy compound is preferably ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether (collectively, "(poly) ethylene glycol diglycidyl ether". It is at least one selected from the group consisting of "ether"), and is more preferably a compound represented by the following formula (1) from the viewpoint of further excellent flexibility of the heat storage molded body 1.

In equation (1), n represents an integer of 1 to 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.

A curing agent may be used or a curing accelerator may be further used to cure the water-soluble epoxy compound. That is, the resin 2 may be a cured product of a composition containing a water-soluble epoxy compound and a curing agent, or may be a cured product of a composition containing a water-soluble epoxy compound, a curing agent and a curing accelerator. The composition is, for example, a thermosetting composition that is cured by heat. The curing agent and curing accelerator are appropriately selected depending on the type of the water-soluble epoxy compound.

As the curing agent, for example, an isocyanate-based curing agent, a phenol-based curing agent, an imidazole-based curing agent, an acid anhydride-based curing agent, a carboxylic acid-based curing agent, an amine-based curing agent and the like are used.

The curing agent is preferably an organic solvent or a curing agent that dissolves in water, and more preferably a curing agent that dissolves in water (water-soluble curing agent). The curing agent is preferably a water-soluble curing agent such as a water-soluble imidazole-based curing agent, a water-soluble carboxylic acid-based curing agent, and a water-soluble amine-based curing agent. These curing agents may be used alone or in combination of two or more.

The curing agent is preferably a water-soluble amine-based curing agent from the viewpoint of excellent reactivity with the water-soluble epoxy compound. When the water-soluble epoxy compound is also soluble in an organic solvent (for example, when the water-soluble epoxy compound is (poly) ethylene glycol diglycidyl ether), the curing agent is an isocyanate-based curing agent, a phenol-based curing agent, or an acid anhydride. It may be a curing agent that dissolves in an organic solvent such as a system curing agent.

Examples of the isocyanate-based curing agent 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'-toluidine diisocyanate (TODI), aromatic diisocyanates such as 4,4'-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate, or a mixture thereof) (XDI), tetramethyl Examples thereof include xylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate, or a mixture thereof) (TMXDI), ω, ω'-diisocyanate-1,4-diethylbenzene and the like. Examples of the isocyanate-based curing agent 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. An aliphatic diisocyanate such as −pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate. , 1,3-Cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (1,3-cyclohexanediisocyanate) Isophorone diisocyanate) (IPDI), methylene bis (cyclohexamethylene diisocyanate) (4,4'-, 2,4'-or 2,2'-methylene bis (cyclohexamethylene diisocyanate), these trans, trans-forms, trans, cis-forms, cis, cis-form or a mixture thereof) (H12MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornan diisocyanate (various isomers or a mixture thereof) (NBDI) , Alicyclic diisocyanate such as bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (H6XDI) and the like.

Examples of the phenolic curing agent include bisphenol A, bisphenol F, bisphenol S, 4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, and dimethyl. Bisphenol 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 , Resolsinol, hydroquinone, pyrogallol, phenols having a diisopropyridene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene; cresols; ethylphenols; butylphenols; octylphenols; bisphenols Novolac resin made from various phenols such as A, bisphenol F, bisphenol S, naphthols, xylylene skeleton-containing phenol novolac resin, dicyclopentadiene skeleton-containing phenol novolac resin, biphenyl skeleton-containing phenol novolac resin, fluorene skeleton-containing phenol novolac resin. , Various novolak resins such as furan skeleton-containing phenol novolak resin and the like.

Examples of the imidazole-based curing agent include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1 -Cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2 -Methylimidazole, 2,3-dihydro-1H-pyrrolo- [1,2-a] benzimidazole, 2,4-diamino-6 (2'-methylimidazole (1')) ethyl-s-triazine, 2, 4-Diamino-6 (2'-undecylimidazole (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- Examples thereof include phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole and the like. From the viewpoint of excellent water solubility, the imidazole-based curing agent is preferably 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, or 1-cyanoethyl-2. -Phenylimidazole.

Examples of the acid anhydride-based curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol anhydride trimellitic anhydride, and biphenyltetracarboxylic acid anhydride. Aromatic carboxylic acid anhydrides such as; aliphatic carboxylic acid anhydrides such as azelaic acid, sebacic acid, dodecanedic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, nagic acid anhydride, het acid anhydride. , Hymic acid anhydride and the like alicyclic carboxylic acid anhydride and the like.

Examples of the carboxylic acid-based curing agent include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid.

Examples of amine-based curing agents include diethylenetriamine, triethylenetetramine, diaminodiphenylmethane, diaminodiphenylsulphon, diaminodiphenylether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5-diaminonaphthalene, and m-xylyl. Aromatic amines such as range amines, ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, aliphatic amines such as polyetherdiamine; dicyandiamide, 1- (o-tolyl) biguanide, etc. Guanidins and the like. The amine-based curing agent is preferably diethylenetriamine or triethylenetetramine from the viewpoint of excellent water solubility.

The content of the curing agent may be, for example, 0.1 part by mass or more or 1 part by mass or more, and 50 parts by mass or less, 20 parts by mass or less, or 10 parts by mass with respect to 100 parts by mass of the water-soluble epoxy compound. It may be:

The heat storage microcapsule 3 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, a "chain" means a linear or a branched chain.

Specifically, the chain saturated hydrocarbon compound is n-decane (C10 (carbon number, 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-tridecan (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-pentacosane (C25, 54 ° C.), n-hexacontane (C26, 56 ° C.), n-heptacosane (C27, 60 ° C.), n-octacosane (C28, 65 ° C.), n-nonakosan (C29, 66 ° C.), n-triacontane (C30, 67 ° C.), n-tetracontane (C30, 67 ° C.) C40, 81 ° C.), n-pentacontane (C50, 91 ° C.), n-hexacontane (C60, 98 ° C.), n-hexacontane (C100, 115 ° C.), etc. Chain saturated hydrocarbon compounds. 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. It may be there.

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, more preferably 40 ° C. or higher, still more 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 microcapsules is measured by 1% when the weight loss of the microcapsules is measured using a differential thermogravimetric simultaneous measuring device (for example, TG-DTA6300 (manufactured by Hitachi High-Tech Science Corporation)). Will be done.

As the material for forming the outer shell, a material having strength according to the use of the heat storage molded product is appropriately selected. The outer shell is preferably made of melamine resin, acrylic resin, urethane resin, silica or the like. Examples of microcapsules having an outer shell containing melamine resin as a main component include ThermoMemory FP-16, FP-25, FP-31, FP-39 manufactured by Mitsubishi Paper Mills Limited, and Riken Resin PMCD manufactured by Miki Riken Kogyo Co., Ltd. -15SP, 25SP, 32SP and the like are exemplified. Examples of microcapsules having an outer shell containing an acrylic resin (polymethylmethacrylate resin) as a main component include Micronal DS5001X and 5040X manufactured by BASF. Examples of microcapsules having an outer shell containing silica as a main component 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 microcapsules, from the viewpoint of further enhancing the heat storage effect, and the microcapsules are damaged due to the volume change of the heat storage component. From the viewpoint of suppressing the above, it is preferably 80% by mass or less, and may be 20 to 80% by mass or 60 to 80% by mass.

The heat storage microcapsules 3 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 microcapsules.

The particle size (average particle size) of the heat-storing microcapsules 3 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. It may be 0.1 to 100 μm, 0.1 to 50 μm, 0.2 to 100 μm, 0.2 to 50 μm, 0.5 to 100 μm, or 0.5 to 50 μm. The particle size (average particle size) of the heat storage microcapsules 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 microcapsules (powder state) is preferably 100 J / g or more, more preferably 150 J / g or more, still more preferably 200 J / g, from the viewpoint of obtaining a heat storage molded product having a higher heat storage density. It is g or more. The heat storage capacity is measured by differential scanning calorimetry (DSC).

From the viewpoint of further enhancing the heat storage effect, the content of the microcapsules is preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 50% by mass or more, particularly preferably 50% by mass or more, based on the total amount of the heat storage molded product. It is 60% by mass or more. The content of the microcapsules is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80, based on the total amount of the heat storage molded body, from the viewpoint of suppressing the microcapsules from falling off from the heat storage molded body. It is less than mass%. The content of the microcapsules is 10 to 90% by mass, 10 to 85% by mass, 10 to 80% by mass, 30 to 90% by mass, 30 to 85% by mass, and 30 to 80% by mass based on the total amount of the heat storage molded body. %, 50-90% by mass, 50-85% by mass, 50-80% by mass, 60-90% by mass, 60-85% by mass, or 60-80% by mass.

Regarding the method for producing microcapsules, from the conventionally known production methods such as the interfacial polymerization method, the in-situ polymerization method, the in-liquid curing coating method, and the coacervate method, an appropriate method is used according to the heat storage component, the shell material, and the like. You can select it.

The heat storage molded product 1 preferably further contains a surface treatment agent from the viewpoint of improving the adhesiveness at the interface between the microcapsules 3 and the resin 2. The surface treatment agent may be, for example, a coupling agent. Coupling agents include aminosilane-based coupling agents, epoxysilane-based coupling agents, phenylsilane-based coupling agents, alkylsilane-based coupling agents, alkenylsilane-based coupling agents, alkynylsilane-based coupling agents, and haloalkylsilane-based coupling agents. Coupling agent, siloxane-based coupling agent, hydrosilane-based coupling agent, silazane-based coupling agent, alkoxysilane-based coupling agent, chlorosilane-based coupling agent, (meth) acrylic silane-based coupling agent, aminosilane-based coupling agent , Isocyanuratesilane-based coupling agent, ureidosilane-based coupling agent, mercaptosilane-based coupling agent, sulfidesilane-based coupling agent, isocyanatesilane-based coupling agent and the like. The coupling agent is preferably an aminosilane-based coupling agent from the viewpoint of reactivity with the resin.

The heat storage molded product 1 can further contain other additives, if necessary. Other additives include, for example, antioxidants, colorants, fillers, crystal nucleating agents, heat stabilizers, heat conductive materials, plasticizers, foaming agents, flame retardants, vibration damping agents, flame retardant aids (eg metals). Oxide) and the like. Other additives may be used alone or in combination of two or more.

The heat storage molded body 1 according to the present embodiment can have a heat storage capacity of, for example, 100 J / g or more by providing the above configuration. Therefore, the heat storage molded product is preferably used as a heat storage material.

Further, the heat storage molded body 1 is excellent in flexibility. In the present specification, "excellent in flexibility" means that one end of the heat storage molded body 1 in the length direction is fixed on a flat surface with respect to a test piece having a length of 50 mm, a width of 5 mm, and a thickness of 3 mm. It means that the height from the flat surface to the other end becomes 10 mm or more when the end is lifted in the thickness direction. When the heat storage molded body 1 is larger than 50 mm in length × 5 mm in width × 3 mm in thickness, a test piece having a predetermined size may be cut out from the heat storage molded body 1.

Subsequently, a method for manufacturing the heat storage molded product will be described. The method for producing a heat storage molded product according to an embodiment includes a preparation step for preparing a curable composition containing the above-mentioned water-soluble epoxy compound and microcapsules, and a molding step for molding the curable composition.

In addition to the water-soluble epoxy compound and microcapsules, the curable composition may further contain the above-mentioned curing agent, may further contain the above-mentioned surface treatment agent, and may further contain water. When the curable composition contains water, the water may be in a state of being separated from the components other than water in the curable composition.

The preparation step includes, for example, a mixing step of mixing the above-mentioned components with a revolution mixer. For example, when the curable composition contains microcapsules, a water-soluble epoxy compound and a curing agent, in the mixing step, for example, a self-revolving mixer is used to first mix the microcapsules and the water-soluble epoxy compound at 1000 to 3000 rpm, 1 to 1. The mixture may be mixed under the condition of 10 minutes, then the curing agent may be added, and the mixture may be further mixed under the condition of 1000 to 3000 rpm for 30 seconds to 10 minutes.

The microcapsules are preferably subjected to the preparation step in the form of an aqueous dispersion previously dispersed in water. That is, in the preparation step, preferably, an aqueous dispersion of microcapsules, a water-soluble epoxy compound, a curing agent containing a water-soluble curing agent, and if necessary, other components such as a surface treatment agent are used. , Prepare a curable composition. The content of the microcapsules in the aqueous dispersion may be, for example, 10% by mass or more and 50% by mass or less.

The content of the water-soluble epoxy compound, microcapsules and curing agent in the curable composition may be the same as the content of the water-soluble epoxy compound, microcapsules and curing agent in the heat storage molded product described above. However, "based on the total amount of the heat storage molded product" should be read as "based on the total amount of the non-volatile content in the curable composition". The "nonvolatile component in the curable composition" means a component that does not volatilize in the volatilization step described later (for example, a water-soluble epoxy compound, microcapsules, a curing agent, etc.).

In the preparation step, after the mixing step, if necessary, a defoaming step of defoaming the cured curable composition after mixing may be further performed. In the defoaming step, for example, defoaming may be performed under the conditions of 1000 to 3000 rpm for 30 seconds to 10 minutes.

In the molding step, for example, the curable composition obtained in the preparation step is poured into a molding die for molding. More specifically, in the molding step, the curable composition is molded by a wet molding method such as a heat melt molding method or a gel casting method. The molding method in the molding step is preferably a gel casting method from the viewpoint that the microcapsules are suitable when they are inexpensive and easily available water-dispersion type microcapsules.

For example, when the curable composition contains water, a volatilization step of volatilizing water may be further carried out after the molding step. In the volatilization step, for example, it may be dried under the conditions of 20 to 30 ° C. and atmospheric pressure for 1 to 10 days, and under the conditions of 60 to 100 ° C. and negative pressure (for example, -0.05 to -0.2 MPa). , May be dried for 1-7 days, or both may be performed.

The heat storage molded body 1 described above can be used in various fields. The heat storage molded body 1 includes, for example, air conditioning equipment (improvement of efficiency of air conditioning equipment) in automobiles, buildings, public facilities, underground streets, etc., piping in factories (heat storage of piping), automobile engine (heat retention around the engine), and the like. Used for electronic parts (preventing temperature rise of electronic parts), fibers of underwear, etc.

Next, an article provided with the heat storage molded body 1 and a method for manufacturing the same will be described by taking an electronic component as an example for providing the heat storage molded body 1.

FIG. 2 is a schematic cross-sectional view showing an embodiment of an article and a method for manufacturing the article. In the method of manufacturing an article of one embodiment, first, as shown in FIG. 2A, an electronic component 11 is prepared as an article to be provided with a heat storage molded body. The electronic component 11 includes, for example, a substrate 12 and a semiconductor chip (heat source) 13 provided on the substrate 12.

Subsequently, as shown in FIG. 2B, the sheet-shaped heat storage molded body 1 is arranged on the substrate 12 and the semiconductor chip 13 so as to be in thermal contact with each of the substrate 12 and the semiconductor chip 13.

As a result, the article 14A including the substrate 12, the semiconductor chip 13, and the heat storage molded body 1 (cured product of the curable composition) provided on the substrate 12 and the semiconductor chip 13 can be obtained.

In the above embodiment, the heat storage molded body 1 is arranged so as to cover the entire exposed surface of the heat source 13, but in the other embodiment, the heat storage molded body is arranged so as to cover a part of the exposed surface of the heat source. You may.

FIG. 3A is a schematic cross-sectional view showing another embodiment of the article. As shown in FIG. 3A, in the article 14B according to the other embodiment, the heat storage molded body 1 comes into contact with (covers a part of) a part of the exposed surface of the semiconductor chip (heat source) 13, for example. May be arranged. The place where the heat storage molded body 1 is arranged (the place where the heat storage molded body 1 contacts the semiconductor chip 13) is a side surface portion of the semiconductor chip 13 in FIG. 3A, but on any surface of the semiconductor chip 13. There may be.

FIG. 3B is a schematic cross-sectional view showing another embodiment of the article. As shown in FIG. 3B, in the article 14C according to the other embodiment, the heat storage molded body 1 is arranged on the surface of the substrate 12 opposite to the surface on which the semiconductor chip 13 is provided. In the present embodiment, the heat storage molded body 1 is not in direct contact with the semiconductor chip 13, but is in thermal contact with the semiconductor chip 13 via the substrate 12. The place where the heat storage molded body 1 is arranged may be on any surface of the substrate 12 as long as it is in thermal contact with the semiconductor chip 13. Even in this case, the heat generated by the heat source (semiconductor chip) 13 is efficiently conducted to the heat storage molded body 1 via the substrate 12, and is suitably stored in the heat storage molded body 1.

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.

The sheet-shaped heat storage molded product used in the examples was produced by the gel casting method as follows. The sheet-shaped molded product used in the comparative example was cured at normal temperature and pressure. Each composition is shown in Table 1.

(Example 1)
In a 50 mL polypropylene container, 25.4 parts by mass of ethylene glycol diglycidyl ether (compound having n of 1 in the formula (1), Denacol EX810, manufactured by Nagase ChemteX Corporation) as a water-soluble epoxy compound, heat-storing microcapsules. Add 175 parts by mass of an aqueous dispersion (content of heat storage microcapsules: 40% by mass, manufactured by Miki Riken Kogyo Co., Ltd., average particle size: 2.7 μm, melting point of heat storage component: 5 ° C), and use a rotation / revolution mixer at 2000 rpm. The mixture was stirred and mixed for 2 minutes to prepare a mixed dispersion of a water-soluble epoxy compound and microcapsules. To this mixed dispersion, 4.6 parts by mass of diethylenetriamine (manufactured by Tokyo Kasei Co., Ltd.) was added as a curing agent, and the mixture was stirred and mixed at 2000 rpm for 1 minute and defoamed at 2200 rpm for 30 seconds to prepare a curable composition. did. Using this curable composition, a molded product was obtained by a gel casting method. Specifically, the curable composition was cast into a molding die and then solidified by an in-situ gelling reaction to obtain a wet cured product. The obtained cured product was dried at 25 ° C. for 3 days and then vacuum dried at 80 ° C. and −0.1 MPa for 3 days to obtain a heat storage molded product.

(Example 2)
28.9 parts by mass of polyethylene glycol diglycidyl ether (compound having n of 22 in the formula (1), Denacol EX861, manufactured by Nagase ChemteX Corporation) was used as the water-soluble epoxy compound, and 1.1 parts by mass of diethylenetriamine was used as the curing agent. A heat storage molded body was produced in the same manner as in Example 1 except that the heat storage molded body was produced.

(Example 3)
Heat storage was performed in the same manner as in Example 1 except that 26.7 parts by mass of sorbitol polyglycidyl ether (Denacol EX614, manufactured by Nagase ChemteX Corporation) was used as the water-soluble epoxy compound and 3.3 parts by mass of ethylene triamine was used as the curing agent. A molded body was produced.

(Comparative Example 1)
To a 50 mL polypropylene container, add 29.1 parts by mass of Epomount (manufactured by Refine Tech Co., Ltd.), 0.9 parts by mass of diethylenetriamine, and 70 parts by mass of heat-storing microcapsules (powder) as a water-insoluble epoxy resin, and rotate. A mixture of epoxy resin and microcapsules was prepared by stirring and mixing with a revolving mixer at 2000 rpm for 3 minutes. This mixture was an extremely small mass of liquid content and could not be molded.

(Comparative Example 2)
To a 50 mL polypropylene container, add 67.9 parts by mass of Epomount (manufactured by Refine Tech Co., Ltd.) and 30 parts by mass of heat-storing microcapsules (powder) as a water-insoluble epoxy resin, and use a rotation / revolution mixer at 2000 rpm for 3 minutes. The mixture was stirred and mixed to prepare a mixed solution of epoxy resin and microcapsules. A varnish was prepared by adding 2.1 parts by mass of diethylenetriamine as a curing agent to this mixed dispersion and stirring and defoaming at 2000 rpm for 1 minute and 30 seconds. This varnish was poured into a metal molding container and cured at 25 ° C. for 24 hours to prepare a heat storage molded product.

[Evaluation of moldability]
The moldability was evaluated with the case where the molded product could be produced (Examples 1 to 3 and Comparative Example 2) as "A" and the case where the molded product could not be produced (Comparative Example 1) as "B". The results are shown in Table 1.

[Evaluation of heat storage]
Each heat storage molded product of Examples 1 to 3 and Comparative Example 2 was measured using a differential scanning calorimetry meter (manufactured by PerkinElmer, model number DSC8500), and the heat storage amount was calculated. Specifically, the temperature is raised to 100 ° C. at 10 ° C./min, held at 100 ° C. for 5 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 area of the melting peak was taken as the amount of heat storage. The results are shown in Table 1.

[Evaluation of flexibility]
From each of the heat storage molded bodies of Examples 1 to 3 and Comparative Example 2, test pieces having a length of 50 mm, a width of 5 mm, and a thickness of 3 mm were prepared. When one end of the test piece in the length direction is fixed on a flat surface and the other end is lifted in the thickness direction, the height from the flat surface to the other end is 10 mm or more without damaging the heat storage molded body. The flexibility was evaluated with "A" when it was lifted and "B" when it was not lifted. The results are shown in Table 1.

[Evaluation of liquid leakage and volatility]
For each of the heat storage molded products of Examples 1 to 3 and Comparative Example 2, the weight change before and after standing for 1000 hours in an air atmosphere at a temperature of 80 ° C. was measured, and the weight reduction rate (%) was measured. The results are shown in Table 1.

As shown in Examples, the heat storage molded product of the present invention is excellent in heat storage amount and moldability, and in addition, can suppress liquid leakage and volatilization. Further, as the water-soluble epoxy compound, when the compound represented by the above formula (1) is used (Examples 1 and 2), as compared with the case where other water-soluble epoxy compounds are used (Example 3), A heat storage molded product having excellent flexibility can be obtained.

On the other hand, when an epoxy resin that is not a water-soluble epoxy compound is used and the same amount of microcapsules as in Examples 1 to 3 is used (Comparative Example 1), a molded product cannot be produced. Further, when the amount of microcapsules is reduced to the extent that a molded product can be produced by using an epoxy resin that is not a water-soluble epoxy compound (Comparative Example 2), the amount of heat storage is inferior to that of Examples 1 to 3.

Since the heat storage molded product on one side of the present invention is excellent in heat storage amount and moldability, it can be used as a molded product exhibiting a sufficient heat storage effect. Further, since the heat storage molded product on the other side of the present invention is also excellent in flexibility, it can be used by being attached to a curved surface of a house, an automobile, or the like.

1 ... Heat storage molded body, 2 ... Resin, 3 ... Heat storage microcapsule, 11 ... Electronic component, 12 ... Substrate, 13 ... Semiconductor chip (heat source), 14A, 14B, 14C ... Article.

Claims (14)

It contains a resin and microcapsules dispersed in the resin and containing a heat storage component.
A heat storage molded product in which the resin contains a cured product of a water-soluble epoxy compound. The heat storage molded product according to claim 1, wherein the water-soluble epoxy compound is a glycidyl ether compound. The heat storage molded product according to claim 1 or 2, wherein the water-soluble epoxy compound is a compound represented by the following formula (1).

[In equation (1), n represents an integer of 1 to 22. ] The heat storage molded product according to any one of claims 1 to 3, wherein the content of the microcapsules is 10 to 80% by mass based on the total amount of the heat storage molded product. The heat storage molded product according to any one of claims 1 to 4, wherein the microcapsules have a particle size of 0.2 to 100 μm. The heat storage molded product according to any one of claims 1 to 5, wherein the content of the resin is 10 to 80% by mass based on the total amount of the heat storage molded product. The heat storage molded product according to any one of claims 1 to 6, which has a heat storage capacity of 100 J / g or more. A curable composition containing a water-soluble epoxy compound and microcapsules containing a heat storage component. The curable composition according to claim 8, wherein the water-soluble epoxy compound is a glycidyl ether compound. The curable composition according to claim 8 or 9, wherein the water-soluble epoxy compound is a compound represented by the following formula (1).

[In equation (1), n represents an integer of 1 to 22. ] The curable composition according to any one of claims 8 to 10, further containing a curing agent. The curable composition according to any one of claims 8 to 11, further containing water. A heat storage molded product containing a cured product of the curable composition according to any one of claims 8 to 12. With a heat source
An article comprising the heat storage molded article according to any one of claims 1 to 7 and 13, which is provided so as to be in thermal contact with the heat source.

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