JP2014189779A - Latent heat storage material composition and latent heat storage material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a latent heat storage material composition unaccompanied, even when solidification-melting phase changes are repeated, by the seepage and phase separation of an organic latent heat storage material and yielding a latent heat storage material having an excellent gel stability.SOLUTION: The provided latent heat storage material composition is a latent heat storage material composition including a thermosetting polyurethane resin obtained by feeding and reacting an organic latent heat storage material (A), a polyisocyanate (B), and a polyester polyol (C) wherein the polyester polyol (C) is a polyester polyol synthesized from raw ingredients including, with respect to the sum of all raw ingredients thereof, 60-90 mass% of an alkenyl group-containing succinic anhydride or succinic acid.

Description

  The present invention relates to a latent heat storage material composition and a latent heat storage body obtained using the same.

  More specifically, the latent heat storage material composition of the present invention is a composition in which an organic latent heat storage material is fixed (gelled) with a thermosetting polyurethane resin (support material) obtained by reacting polyisocyanate and polyester polyol. The polyester polyol contains a polyester polyol obtained by using a specific amount of (anhydrous) succinic acid having an alkenyl group as a synthetic raw material.

  It has been a long time since there was concern about the depletion of fossil energy resources centered on oil on a global scale. For this reason, a technology for storing thermal energy, that is, a heat storage technology, has attracted attention as a new technology for solving recent energy problems.

  Thermal storage technology is a technology that makes effective use of natural energy, such as solar heat and geothermal heat, or residual heat and exhaust heat generated by air conditioning equipment. It is attracting attention as a technology that uses it as a heat source and reduces power consumption during the day. In addition, the use of heat storage technology increases energy efficiency over conventional water-cooled systems such as building air conditioning, vehicle air conditioning, and house interiors.

  Examples of the heat storage material used in such a heat storage technology include a sensible heat storage material, a latent heat storage material, and a chemical heat storage material. Among these, latent heat storage materials using latent heat due to phase change of substances (phase change between solidification and melting) are already being used in many fields.

  A latent heat storage material stores heat (referred to as "heat storage") when a substance undergoes a phase change (melting) from the solid phase to the liquid phase, and releases heat when the phase changes (solidifies) from the liquid phase to the solid phase ("heat dissipation" ”) To store and dissipate heat.

  In Europe, the use of latent heat storage materials is recommended as part of measures to regulate carbon dioxide emissions. In North America, latent heat storage materials are already used in some hybrid cars. In Japan, it is attracting attention from various fields as an eco-friendly material with low environmental impact. For example, it is used in various fields such as thermal storage floor heating and air conditioning systems, facilities, electrical and electronics, industry, housing, and transportation. Is expected to expand.

  As one form for effectively using the latent heat storage material, for example, there is a method in which the latent heat storage material is enclosed in a sealed laminate sheet or plastic case to form and use a latent heat storage body. Such a method has an advantage that the content of the latent heat storage material per unit volume can be increased. In addition, there are various forms depending on applications and purposes, such as gel, granular, slurry, capsule, and bead.

  The latent heat storage material is roughly classified into an “inorganic latent heat storage material” using an inorganic compound as a main component and an “organic latent heat storage material” using an organic compound.

  Examples of the inorganic latent heat storage material include sodium sulfate decahydrate, sodium carbonate decahydrate, sodium hydrogen phosphate dodecahydrate, sodium thiosulfate pentahydrate, calcium chloride hexahydrate, sodium acetate 3 Examples thereof include hydrated salts such as hydrates. In general, an inorganic latent heat storage material has advantages such as (1) being cheaper than an organic latent heat storage material and (2) being incombustible or incombustible in terms of safety and disaster prevention. However, the inorganic latent heat storage material has disadvantages such as (1) difficulty in adjusting the melting point, and (2) relatively strong corrosiveness to metals, and there has been a problem that the intended use is limited.

  Examples of the organic latent heat storage material include aliphatic hydrocarbons (for example, paraffin compounds such as normal paraffin), long chain alcohols, long chain fatty acids, long chain fatty acid esters, fatty acid triglycerides, polyether compounds, and the like.

  Among these, long-chain fatty acids and long-chain fatty acid esters (1) can be adjusted over a wide range of basic performance (heat storage temperature, thermal conductivity, melting point, etc.) according to the purpose of use by containing appropriate amounts. There are many advantages such as (2) less deterioration of itself even if the phase change is repeated many times, and (3) less corrosiveness to metals.

  However, since long-chain fatty acids and long-chain fatty acid esters have a lower heat storage density than paraffin compounds, they have not been satisfactory as materials capable of efficient heat energy exchange.

  Among the above organic latent heat storage materials, aliphatic hydrocarbons, especially normal paraffins, are used for (1) wide adjustment of basic performance (heat storage temperature, thermal conductivity, melting point, etc.) by including appropriate amounts. Many things such as (2) high heat storage density, (3) almost no deterioration of itself even after repeated phase changes, and (4) no corrosiveness to metals. There are advantages.

  However, normal paraffins with 17 or less carbon atoms are themselves flammable dangers (Class 3 flammable liquids of the Fire Service Act), so normal paraffins are fixed at room temperature (gelation) ) And how to treat it as non-dangerous goods has been studied.

  Moreover, in such a latent heat storage material composition containing normal paraffin, (1) when the organic latent heat storage material is contained at a high concentration, the gel stability is inferior, and (2) the organic latent heat storage material There were problems such as immobilization (gelation) material having poor compatibility and causing problems such as oozing and phase separation.

Various proposals have been made to improve such problems.
For example, an organic latent heat storage material, an organically treated layered clay mineral, a polyol having 3 or more OH groups in a molecule, and having a hydroxyl value of 15 KOHmg / g or more and 40 KOHmg / g or less, an isocyanate compound, and a polyol And a heat storage body in which the mixing ratio of the isocyanate compound is 1.5 or more and 8.0 or less in an NCO / OH ratio is known (see, for example, Patent Document 1).

  The heat storage material described in Patent Document 1 has a high heat storage material content rate, good heat storage performance and sustainability of the heat storage performance, and the heat storage material has increased over time despite having a high heat storage material content rate. There is no leakage.

  However, in Patent Document 1, it is difficult to say that the heat storage material content rate is 75% at the maximum, and the heat storage material content rate is high, and an organic latent heat storage material (for example, paraffin compound) having a large heat capacity is actually used. There was a problem that the heat storage performance was inferior.

  Moreover, the composition for thermal storage materials containing an elastomer and a C8-C14 paraffin compound is known (for example, refer patent document 2).

  The composition for a heat storage material described in Patent Document 2 has a small supercooling phenomenon without adding a nucleating agent, and can store and release heat in a temperature range of, for example, −60 to 6 ° C., and has fluidity at room temperature. In addition to being small, the fluidity during molding is excellent, and the bleedability of the paraffin compound is low even in the operating temperature range of the heat storage material, and the shape retention is good.

  However, in Patent Document 2, a gas phase that adversely affects heat exchange such as air pockets (voids, cavities) and depressions is generated and stays due to molding shrinkage of the organic latent heat storage material by repeating solidification and melting phase changes. As a result, there were problems such as a decrease in heat storage performance.

  Various methods are known as a method of immobilizing (gelling) a latent heat storage material by mixing a polymer resin as a support material and the latent heat storage material.

  Examples of such polymer resins (supporting substances) include acrylic resins, polyester resins, silicon resins, epoxy resins, polyvinyl alcohol resins, amino resins, phenol resins, fluororesins, alkyd resins, melamine resins, polycarbonate resins, fluorine Resin, vinyl acetate resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicone resin, silicon-modified acrylic resin, ethylene / vinyl acetate / vinyl versatic acid ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin Solvent-soluble resin such as AS resin, water-soluble resin, water-dispersed resin, solventless resin, chloroprene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, methyl methacrylate-butadiene rubber, butadiene Rubber Like synthetic rubber or the like is.

  However, in a latent heat storage body using a conventional polymer material (support material) and a latent heat storage material composition containing an organic latent heat storage material (particularly normal paraffin), (1) When normal paraffin is mixed at a high concentration In addition, it has poor compatibility and poor phase stability due to phase separation. (2) The processing temperature is high and the molding shrinkage of the latent heat storage element is large, which adversely affects heat exchange such as air pockets (voids and cavities) and depressions. However, there is still a problem to be solved, such as the generation of a gas phase that causes heat retention and a decrease in heat storage performance.

JP 2011-208121 A JP 2013-6937 A

  The purpose of the present invention is to achieve compatibility (there is no oozing or phase separation of the organic latent heat storage material), gel stability (organic latent heat storage material), no matter how many times the phase change between solidification and melting is repeated. It is to provide a latent heat storage material composition that exhibits excellent performance, such as being able to maintain a stable gel state even when mixed at a high concentration, and a latent heat storage body obtained using the same.

  As a result of diligent studies to solve the above-mentioned problems, the inventors of the present invention have a latent heat storage material composition containing an organic latent heat storage material and a thermosetting polyurethane resin obtained by reacting a polyisocyanate and a specific polyester polyol. It has been found that a latent heat storage material composition and a latent heat storage material having an excellent performance such as compatibility and gel stability can be obtained. It came to be completed.

  That is, the present invention is an organic latent heat storage material (A), and a latent heat storage material composition containing a thermosetting polyurethane resin charged and reacted with a polyisocyanate (B) and a polyester polyol (C), The polyester polyol (C) is a polyester polyol synthesized from a raw material containing 60 to 90% by mass of (anhydrous) succinic acid having an alkenyl group, and relates to a latent heat storage material composition.

  Moreover, this invention relates to the latent heat storage body characterized by being obtained using the said latent heat storage material composition.

  The latent heat storage material composition of the present invention is capable of phase change between solidification and melting by having the above configuration, and the organic latent heat storage material (A) and the thermosetting polyurethane resin are excellent in compatibility and cured. Excellent performance such as gel stability can be achieved.

  Moreover, the latent heat storage body of the present invention is obtained using the latent heat storage material composition, the organic latent heat storage material (A) and the thermosetting polyurethane resin are excellent in compatibility, and the organic latent heat storage material is used. Since stable gel formation can be maintained even when mixed at a high concentration, the organic latent heat storage material (A) does not cause problems such as bleeding and phase separation no matter how many times the phase change between solidification and melting is repeated. For this reason, for example, it is useful for a wide range of applications such as heat storage type floor heating and air conditioning systems, as well as various fields such as facilities, electric and electronics, industry, housing and transportation.

  The latent heat storage material composition of the present invention contains an organic latent heat storage material (A) and a thermosetting polyurethane resin obtained by reacting a polyisocyanate (B) and a polyester polyol (C). Each configuration will be described in detail below.

<(A) Organic latent heat storage material>
First, the organic latent heat storage material (A) which is a main component in the latent heat storage material composition of the present invention will be described below.

  In the latent heat storage material composition, the content of the organic latent heat storage material (A) is the total amount of the organic latent heat storage material (A) and the charged amount of the polyisocyanate (B) and the polyester polyol (C). On the other hand, it is preferably in the range of 30 to 90% by mass, more preferably in the range of 50 to 90% by mass, and still more preferably in the range of 70 to 90% by mass. If the content of (A) is within such a range, a latent heat storage material composition that makes the best use of the heat capacity can be obtained.

  Examples of the organic latent heat storage material (A) include aliphatic hydrocarbons, long chain alcohols, long chain fatty acids, long chain fatty acid esters, and fatty acid triglycerides. These may be used alone or in combination of two or more.

  As the aliphatic hydrocarbon, for example, an aliphatic hydrocarbon having 8 to 36 carbon atoms can be used, and specifically, n-decane (melting point-30 ° C), n-undecane (melting point-25 ° C). , N-dodecane (melting point −8 ° C.), n-tridecane (melting point −5 ° C.), pentadecane (melting point 6 ° C.), n-tetradecane (melting point 10 ° C.), n-hexadecane (melting point 17 ° C.), n-heptadecane ( N-octadecane (melting point 28 ° C.), n-nonadecane (melting point 32 ° C.), eicosane (melting point 36 ° C.), docosane (melting point 44 ° C.), and mixtures thereof. Etc.

  As the long-chain alcohol, for example, a long-chain alcohol having 8 to 36 carbon atoms can be used. Specifically, capryl alcohol (melting point: 7 ° C.), lauryl alcohol (melting point: 24 ° C.), myristyl alcohol (melting point: 38 ° C), stearyl alcohol (melting point: 58 ° C), and the like.

  As the long-chain fatty acid, for example, a long-chain fatty acid having 8 to 36 carbon atoms can be used. Specifically, octanoic acid (melting point: 17 ° C.), decanoic acid (melting point: 32 ° C.), dodecanoic acid (melting point: 44 ° C), fatty acids such as tetradecanoic acid (melting point 50 ° C), hexadecanoic acid (melting point 63 ° C), octadecanoic acid (melting point 70 ° C), and the like.

  As the long-chain fatty acid ester, for example, a long-chain fatty acid ester having 8 to 36 carbon atoms can be used. Specifically, methyl laurate (melting point 5 ° C.), methyl myristate (melting point 19 ° C.), palmitic acid Examples include methyl acid (melting point: 30 ° C.), methyl stearate (melting point: 38 ° C.), butyl stearate (melting point: 25 ° C.), and methyl arachidate (melting point: 45 ° C.).

  Examples of the fatty acid triglyceride include vegetable oils such as coconut oil and palm kernel oil, and medium-chain fatty acid triglycerides and long-chain fatty acid triglycerides that are refined processed products thereof.

  Among the organic latent heat storage materials (A), preferably an aliphatic hydrocarbon having 8 to 36 carbon atoms, a long chain alcohol having 8 to 36 carbon atoms, a long chain fatty acid having 8 to 36 carbon atoms, and the number of carbon atoms. Long chain fatty acid esters having 8 to 36 carbon atoms, more preferably aliphatic hydrocarbons having 8 to 36 carbon atoms, and long chain fatty acid esters having 8 to 36 carbon atoms, still more preferably 8 to 36 carbon atoms. It is an aliphatic hydrocarbon.

  Among the organic latent heat storage materials (A), aliphatic hydrocarbons having 8 to 36 carbon atoms have a large amount of latent heat and undergo phase change between solidification and melting within a practical temperature range. In particular, normal paraffins, which are straight-chain saturated aliphatic hydrocarbons having 8 to 36 carbon atoms, preferably 15 to 36 carbon atoms, can be suitably used as the latent heat storage material.

  The phase change temperature of the organic latent heat storage material (A) can be set according to the application, but is usually preferably in the range of −60 to 150 ° C., more preferably in the range of −10 to 60 ° C. More preferably, it is the range of 25-55 degreeC. If the phase change temperature is within such a range, it can be applied to a wide range of applications and can exhibit excellent performance such as compatibility and gel stability.

  In addition, the phase change temperature of the organic latent heat storage material (A) varies as described above depending on the type of the organic latent heat storage material, so that an appropriate organic latent heat storage material can be selected according to the purpose or a plurality of organic latent heat storage materials can be used. What is necessary is just to mix | blend a thermal storage material and to adjust various performances, such as melting | fusing point, compatibility, and gel stability.

<(B) Polyisocyanate>
Next, the polyisocyanate (B) used essentially in the latent heat storage material composition of the present invention will be described below.

  The “polyisocyanate” in the present invention is a reactive compound having two or more isocyanate groups (hereinafter also referred to as “NCO groups”) in the molecule. Any known polyisocyanate can be used as the polyisocyanate (B), and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, and modified products thereof. These may be used alone or in combination of two or more.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), Aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI), 4,4′-diphenyl ether diisocyanate, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof) (TMXDI), ω, and the like ω'- diisocyanate-1,4-diethylbenzene.

  Examples of the aliphatic polyisocyanate 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-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate Group diisocyanate and the like.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl. 3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis (cyclohexyl isocyanate, these trans, trans-form, trans, cis-form, cis, cis-form, or a mixture thereof)) (H12MDI), methylcyclohexane diisocyanate (methyl-2,4-cycl Hexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) And cycloaliphatic diisocyanates such as cyclohexane or a mixture thereof (H6XDI).

  In the present invention, as the polyisocyanate (B), in addition to the polyisocyanate, a polyisocyanate derivative, an isocyanate group-terminated prepolymer, and the like can be used as a modified product.

  Examples of the polyisocyanate derivative include a multimer (for example, a dimer, a trimer (for example, an isocyanurate-modified product, an iminooxadiazinedione-modified product), a pentamer of the above-described polyisocyanate monomer, Heptamers, etc.), allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-described polyisocyanate monomer and low molecular weight polyol described later), polyol-modified products (for example, polyisocyanate monomer and the like) Polyol modified products (alcohol adducts, etc.) produced by reaction with low molecular weight polyols described later), biuret modified products (for example, biuret modified products produced by reaction of the above polyisocyanate monomer with water or amines) Etc.), modified urea (for example, the above-mentioned polyisocyanate monomer and dia Modified with urea, etc.), oxadiazine trione modified (for example, oxadiazine trione produced by reaction of polyisocyanate monomer and carbon dioxide), carbodiimide modified (above) Carbodiimide modified products produced by decarboxylation condensation reaction of the polyisocyanate monomer), uretdione modified products, uretonimine modified products, and the like.

  The above-mentioned isocyanate group-terminated prepolymer is a urethane prepolymer having at least two isocyanate groups at the molecular ends, and is a polyisocyanate (polyisocyanate monomer, polyisocyanate derivative, and polyisocyanate-terminated prepolymer selected from An isocyanate, preferably a polyisocyanate selected from a polyisocyanate monomer and a polyisocyanate derivative) and a polyester polyol (and a low molecular weight polyol if necessary) (hereinafter referred to as a polyol component) described later, The equivalent ratio (NCO / OH) can be obtained by a urethanization reaction at a ratio of greater than 1, preferably 1.5 to 50.

  As the polyisocyanate (B), since most of the organic latent heat storage material (A) is hydrophobic, the use of a highly polar aromatic polyisocyanate may reduce compatibility and gel stability. . Therefore, as the polyisocyanate (B), it is preferable to use an aliphatic polyisocyanate, an alicyclic polyisocyanate, or a modified product thereof from the viewpoint of developing good compatibility and gel stability.

  These polyisocyanate derivatives can be used alone or in combination of two or more.

<(C) Polyester polyol>
Next, the polyester polyol (C), which is an essential component of the latent heat storage material composition of the present invention, will be described below.

  The polyester polyol (C) may be either a polyester polyol having no aromatic skeleton or a polyester polyol having an aromatic skeleton.

  The polyester polyol (C) used in the present invention is produced according to a conventional method using a polyvalent carboxylic acid (c1) and a polyhydric alcohol (c2) as reaction raw materials. As the polyvalent carboxylic acid (c1), (Anhydrous) succinic acid having an alkenyl group is essential.

  As used herein, the term “(anhydrous) succinic acid having an alkenyl group” means both succinic anhydride having an alkenyl group and succinic acid having an alkenyl group, unless otherwise specified. Further, (anhydrous) succinic acid means both succinic anhydride and succinic acid unless otherwise specified.

  The (alkenyl) succinic acid having an alkenyl group can also be used as a reactive acid derivative such as a lower alkyl ester (methyl ester, ethyl ester, etc.), acid halide or the like.

  The succinic anhydride having an alkenyl group is a compound represented by the following structural formula [1]. In the following structural formula [1], R and R ′ each independently represents an alkyl group or hydrogen, and the alkenyl group (RCH═CR′—) preferably has 8 to 50 carbon atoms, More preferably, it is the range of 15-30.

Structural formula [1]

  The succinic acid having an alkenyl group is a compound represented by the following structural formula [2]. In the following structural formula [2], R and R ′ each independently represents an alkyl group or hydrogen, as described above, and the alkenyl group (RCH═CR′—) preferably has 8 to 8 carbon atoms. It is the range of 50, More preferably, it is the range of 15-30.

Structural formula [2]

  The amount of (anhydrous) succinic acid having an alkenyl group in the polyester polyol (C) is the total amount of raw materials of the polyester polyol (C) [the amount of polyvalent carboxylic acid (c1) and polyhydric alcohol (c2) used. The total]] is in the range of 60 to 90 mass%, preferably in the range of 70 to 90 mass%. If the amount of the alkenyl group-containing (anhydrous) succinic acid is within the range, the affinity with the organic latent heat storage material (A) is increased, and excellent performance without causing problems such as phase separation and exudation. Can be expressed. Here, the usage amount of (anhydrous) succinic acid having an alkenyl group includes the usage amount of the above acid derivative of (anhydrous) succinic acid having an alkenyl group.

  However, when the amount of succinic acid having an alkenyl group in the raw material of the polyester polyol (C) is less than 60% by mass relative to the total amount of the raw material of the polyester polyol (C), organic Affinity with the latent heat storage material (A) is lowered, and phase separation and oozing occur. Moreover, when it exceeds 90 mass%, the design of the target polyester polyol (C) becomes difficult, and the object of the present invention cannot be achieved.

  In the present invention, when synthesizing the polyester polyol (C), the polyhydric carboxylic acid is added to the succinic anhydride having an alkenyl group, which is an essential raw material, as long as the other polycarboxylic acid is not hindered by the object of the present invention. It may be used as (c1).

  The other polyvalent carboxylic acid may or may not have an aromatic skeleton, and may be a polyvalent carboxylic acid having no aromatic skeleton (aliphatic polyvalent carboxylic acid, alicyclic polyvalent carboxylic acid). Acid) can also be used.

  Examples of the other polycarboxylic acids include aliphatic polycarboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, pimelic acid, suberic acid, dodecanedicarboxylic acid, maleic acid, and fumaric acid. Or 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, alicyclic polyvalent carboxylic acid such as 1,4-cyclohexanedicarboxylic acid; or orthophthalic acid, isophthalic acid , Aromatics such as terephthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid A polyvalent carboxylic acid is mentioned. These may be used alone or in combination of two or more.

  As the other polyvalent carboxylic acids, polyvalent carboxylic acids having no aromatic skeleton (aliphatic polyvalent carboxylic acids, alicyclic polyvalent carboxylic acids) are improved in compatibility, exudation and phase. It is more preferable from the viewpoint of prevention of separation.

  In addition, for example, polycarboxylic acids such as trimellitic acid and pyromellitic acid can be used as the polyvalent carboxylic acid (c1) as long as the object of the present invention is not impaired.

  In the present invention, in addition to the above polyvalent carboxylic acids, reactive acid derivatives such as acid anhydrides, lower alkyl esters (such as methyl esters and ethyl esters), and acid halides can also be used. In calculating the content of (anhydrous) succinic acid having an alkenyl group, these acid derivatives are also calculated as polyvalent carboxylic acid (c1) as a raw material component of the polyester polyol (C).

  Further, the polyhydric alcohol (c2), which is a raw material for the synthesis of the polyester polyol (C), may or may not have an aromatic skeleton, and a polyhydric alcohol (aliphatic having no aromatic skeleton). (Polyhydric alcohol, alicyclic polyhydric alcohol) can also be used.

  Examples of the polyhydric alcohol (c2) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, trimethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2-butyl-2- Aliphatic diols such as ethyl-1,3-propanediol and 2-methyl-1,3-propanediol; or alicyclics such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and hydrogenated bisphenol A Diol; or bis Phenol A, bisphenol S, fluorinated bisphenol A, chlorinated bisphenol A, brominated bisphenol A, and aromatic diols such as alkylene oxide adducts of bisphenols are exemplified. These may be used alone or in combination of two or more.

  As the polyhydric alcohol (c2), which is a raw material for the synthesis of the polyester polyol (C), polyhydric alcohols (aliphatic polyhydric alcohols, alicyclic polyhydric alcohols) having no aromatic skeleton are more organic latent heat. It is preferable from the viewpoints of improving compatibility with the heat storage material (A) and preventing bleeding and phase separation.

  In this invention, it is preferable to use the polyfunctional compound which has 3 or more of hydroxyl groups in the range which does not inhibit the objective of this invention as the polyhydric alcohol (c2) which is a synthetic raw material of the said polyester polyol (C).

  The usage amount of the polyfunctional compound having three or more hydroxyl groups is based on the total amount of the synthesis raw material of the polyester polyol (C) [the total usage amount of the polyvalent carboxylic acid (c1) and the polyhydric alcohol (c2)]. The range is preferably 0.5 to 15% by mass, more preferably 2 to 10% by mass. If the amount of the polyfunctional compound used is within such a range, better gel stability can be expressed.

  Examples of the polyfunctional compound having three or more hydroxyl groups include trimethylolpropane (TMP), trimethylolethane, glycerin, pentaerythritol, and sorbitol. Among these, from the viewpoint of excellent strength and stability Trimethylolpropane is preferred.

  The polyester polyol (C) is superior in compatibility with the organic latent heat storage material (A) (especially normal paraffin), and causes problems such as exudation and phase separation even if the phase change between solidification and melting is repeated. Since it is difficult, a polyester polyol having no aromatic skeleton is more preferable.

  What is necessary is just to set the number average molecular weight (henceforth "Mn") of the said polyester polyol (C) according to a use, Preferably it is the range of 1000-100000, More preferably, it is the range of 5000-30000. If the Mn in the above (C) is within such a range, the thermosetting polyurethane resin obtained by reacting the above (B) and the above (C) has excellent compatibility with the organic latent heat storage material (A), and phase separation. It is possible to obtain a latent heat storage material composition that does not ooze out and has good reactivity, curability, and excellent gel stability.

  For the synthesis of the polyester polyol (C), a catalyst, a polymerization inhibitor or the like can be used as necessary.

  In the present invention, a lactone (for example, ε-caprolactone, γ-butyrolactone, etc.) is produced together with the polyester polyol (C) obtained by the synthesis reaction of the polyvalent carboxylic acid (c1) and the polyhydric alcohol (c2). Ring-opening addition-polymerized polyester polyols, acrylic polyols, polyolefin polyols, castor oil-based polyols, polyether polyols, polycarbonate polyols, low molecular weight polyols and the like can also be used in combination with the polyester polyol (C) as a polyol (C ′). . When calculating the content of (anhydrous) succinic acid having an alkenyl group, these polyols (C ′) are also included as raw material components of the polyester polyol (C).

  Examples of the polyether polyol include polyethylene glycol (PEG), polypropylene glycol (PPG), polyethylene propylene glycol (PEPG), polytetramethylene glycol (PTMG), or at least glycerin, trimethylolpropane, pentaerythritol, sorbitol, and the like. Examples thereof include poly (oxyalkylene) glycols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide using a compound having three or more hydroxyl groups as a starting material. Among these, polytetramethylene glycol (PTMG, Mn = 650 to 2000) is preferable. The polyether polyol may have any of linear, branched, and cyclic structures.

  As said polycarbonate polyol, the polyol obtained by esterifying carbonic acid and an aliphatic polyol etc. can be used, for example. Specifically, diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol (PTMG), dimethyl carbonate and phosgene And the like. These may be used alone or in combination of two or more.

  Examples of the low molecular weight polyol include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, 1,6-hexanediol, neopentyl glycol, 1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 3-methyl-1,5-pentanediol, 2 -Aliphatic diols such as butyl-2-ethyl-1,3-propanediol and 2-methyl-1,3-propanediol; or 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A Such as alicyclic diols It is below. The low molecular weight polyol may have a linear, branched, or cyclic structure.

  The molecular weight of the low molecular weight polyol is preferably in the range of 62 to 300, more preferably in the range of 62 to 200. If the molecular weight of the low molecular weight polyol is within such a range, the reactivity can be controlled when used in combination with the polyester polyol (C) by the synthesis reaction of the polyvalent carboxylic acid (c1) and the polyhydric alcohol (c2). This is preferable because it can be more easily performed.

<Latent heat storage material composition>
The latent heat storage material composition of the present invention comprises a thermosetting polyurethane resin (supported) obtained by reacting the organic latent heat storage material (A) (particularly normal paraffin) with the polyisocyanate (B) and the polyester polyol (C). The polyester polyol (C) contains a polyester polyol obtained by essentially using (anhydrous) succinic acid having an alkenyl group as a raw material. Features. The latent heat storage material composition of the present invention may further contain the polyol (C ′). In the description of the following specification, when the latent heat storage material composition contains the polyol (C ′), the polyol (C ′) is included in the polyester polyol (C) as the polyester polyol (C). ing.

  In addition, the latent heat storage material of the present invention is obtained using the latent heat storage material composition, and the organic latent heat storage material (A) is compatible (organic latent heat storage material) no matter how many times the phase change between solidification and melting is repeated. ) And gel stability (a stable gel state can be maintained even when the organic latent heat storage material is mixed at a high concentration). The organic latent heat storage material (A) (particularly normal paraffin) can be obtained by fixing (gelling) with a thermosetting polyurethane resin obtained by reacting the polyisocyanate (B) and the polyester polyol (C). .

  In the latent heat storage material composition of the present invention, when (anhydrous) succinic acid having an alkenyl group is used as an essential raw material of the polyester polyol (C), all raw materials of the polyester polyol (C) [polyol (C ′) are used. The polyester polyol (C) used in the range of 60 to 90% by mass of [including polyol (C ′)] is used. Thereby, when the said latent heat storage material composition hardens | cures, the phase change of solidification and a fusion | melting is possible, and excellent performances, such as compatibility and gel stability, can be expressed.

  In the latent heat storage material composition of the present invention, the polyisocyanate (B) and the polyester polyol (C) undergo a urethanation reaction to form a thermosetting polyurethane resin. The thermosetting polyurethane resin in the latent heat storage material composition is further increased in molecular weight and crosslinked to form a three-dimensional network structure, which is stabilized by incorporating the organic latent heat storage material (A) therein. The gel has a structure.

  In the present invention, the polyisocyanate (B) is usually charged in a molar ratio (hereinafter referred to as [NCO / OH]) with respect to the polyester polyol (C), mixed and reacted. ,preferable.

  [NCO / OH] may be set in consideration of target physical properties, product quality, reaction behavior, and the like, and is not particularly limited, but is preferably in a range of 1/1 to 2/1 molar ratio. Preferably it is the range of 1.0 / 1.0-1.3 / 1.0.

  Examples of the method for producing the latent heat storage material composition of the present invention include [Method 1] and [Method 2]. Note that the present invention is not limited to these methods.

[Method 1]
In an inert atmosphere, an organic latent heat storage material (A) (for example, normal paraffin) from which moisture has been removed and a polyester polyol (C) are charged in an inert atmosphere, and stirring and mixing are started. Charge the isocyanate (B) by an appropriate method such as dripping, splitting, or lump while paying careful attention to abnormal reactions (rapid heat generation, bumping, etc.), and react until the hydroxyl groups of the polyester polyol (C) are substantially gone. How to continue.

[Method 2]
A part of the organic latent heat storage material (A) (for example, normal paraffin) from which moisture has been removed and polyester polyol (C) are charged in a reaction vessel under an inert atmosphere, stirring and mixing are started, and the internal temperature is adjusted. However, an abnormal reaction (rapid heat generation, bumping, etc.) can be obtained by an appropriate method such as dripping, dividing or batching a mixture of part of the organic latent heat storage material (A) (for example, normal paraffin) and polyisocyanate (B). A method in which the reaction is continued until the hydroxyl groups of the polyester polyol (C) are substantially eliminated, while charging with sufficient care.

  The latent heat storage material composition of the present invention is usually produced by reaction in the absence of a solvent, but may be reacted in a solvent.

  When making it react in a solvent, what is necessary is just to use the solvent which does not inhibit reaction, and the kind is not specifically limited. It is desirable to remove the solvent used for the reaction by an appropriate method such as a vacuum batch method or a thin film distillation method during or after the reaction.

  In the present invention, the reaction conditions (temperature, time, pressure, etc.) of the polyisocyanate (B) and the polyester polyol (C) in the presence of the organic latent heat storage material (A) (for example, normal paraffin) are safety, reaction behavior. The reaction temperature may be set in a range that can be normally controlled in consideration of product quality and the like, and is not particularly limited. However, the reaction temperature is preferably in the range of 20 to 100 ° C., and the reaction time is in the range of 4 to 60 hours. . The pressure may be normal pressure, increased pressure, or reduced pressure. By this reaction, the thermosetting polyurethane resin is crosslinked, and a gel-like body (for example, paraffin gel) in which the organic latent heat storage material (A) is supported in the crosslinked body is obtained.

  As the reaction method, for example, a known reaction method such as batch, semi-continuous or continuous can be adopted, and it is not particularly limited.

  Moreover, a well-known urethanation catalyst can be used as needed. The catalyst can be appropriately added at any stage such as a raw material charging step and a reaction step. Moreover, the addition method of a catalyst is not specifically limited, such as lump, division | segmentation, and continuous.

  The reaction is preferably performed in an atmosphere of an inert gas such as nitrogen or argon, but may be performed in a dry air atmosphere or under conditions that do not contain moisture, such as sealed conditions.

  In the latent heat storage material composition of the present invention, various known additives can be used at any stage of the production process without departing from the object of the present invention.

  Examples of such additives include foam stabilizers, antioxidants, defoamers, abrasive grains, fillers, pigments, dyes, colorants, thickeners, surfactants, flame retardants, plasticizers, lubricants, charging agents. Known agents such as an inhibitor, a heat stabilizer, a tackifier, a curing catalyst, a stabilizer, a silane coupling agent, and a wax can be used. The additive is merely an example, and the type and amount used are not particularly limited as long as the object of the present invention is not impaired.

<Latent heat storage body>
The latent heat storage body of the present invention is obtained using the latent heat storage material composition, and the shape thereof is, for example, a sheet shape, a rod shape (stick shape), a needle shape, a spherical shape, a square shape (cube shape), a capsule shape, There are various types such as beads and powders depending on the purpose of use, and there is no particular limitation. The latent heat storage body of the present invention is the above-described gel-like body in which the thermosetting polyurethane resin is crosslinked and the organic latent heat storage material (A) is supported in the crosslinked body.

  In the present invention, if a sheet-like latent heat storage body is listed as a representative example, the latent heat storage body does not break even if it is curved for excellent flexibility, and even if it is cut, the organic latent heat storage is from the cut surface. Since the material (A) does not leak out, there is no fear of external contamination and leakage, and it can be used safely, which is preferable.

  Moreover, the sheet-like latent heat storage body can also be laminated | stacked according to the intended purpose on the single side | surface or both surfaces of the said sheet-like latent heat storage body.

  Further, the thickness of the sheet-like latent heat storage body is not particularly limited and may be appropriately set according to the purpose of use, but is usually preferably in the range of 1 to 100 mm.

  The latent heat storage body of the present invention is an industrial product such as a wall material of a building such as a house or a building, an interior / exterior material such as a ceiling material, a floor material, a floor heating system, an interior material such as a vehicle, or a machine / equipment. , Thermoelectric conversion system, heat transfer medium, refrigeration / freezer, bathtub / bathroom, cooler box, heat insulation sheet, anti-condensation sheet, electrical product, OA equipment, plant, tank, clothing, curtain, carpet, bedding, daily necessities, etc. It can also be used as a material to be used.

  What is necessary is just to set the phase change temperature of a latent heat storage material (A) for the latent heat storage body of this invention according to a use objective. For example, when used as an interior / exterior material for a building, a latent heat storage material (A) having a melting point of 15 ° C. to 30 ° C. may be selected and used. Moreover, when using for floor heating, the thing of 25 to 40 degreeC melting | fusing point of a latent-heat storage material (A) is selected, and when using as clothing or bedding, a thing with melting | fusing point of 25 to 35 degreeC, vehicles, etc. When used as an interior material, the melting point is 15 ° C. to 30 ° C., when used for a refrigerator, the melting point is −10 ° C. to 5 ° C., when used for a freezer, the melting point is −30 ° C. to −10 ° C. Each may be selected and used by adding a thermosetting polyurethane resin obtained by reacting the polyisocyanate (B) and the polyester polyol (C) to a reaction-cured resin.

  In addition, the latent heat storage body of the present invention exhibits excellent heat storage and heat insulation properties by laminating heat insulators. For example, building wall materials, ceiling materials, flooring materials, refrigerators / freezers, bathtubs, etc. -By applying it to bathrooms, cooler boxes, etc., the temperature in the space can be kept at an optimum temperature against changes in the external environment temperature, and energy saving can be achieved.

  Examples of such a heat insulator include polystyrene foam, polyurethane foam, acrylic resin foam, phenol resin foam, polyethylene resin foam, foam rubber, glass wool, rock wool, foam ceramic, etc., or a composite thereof. Etc.

  In addition, the latent heat storage body of the present invention can be laminated with a heat conductor, for example, a glass board, a resin board such as an acrylic resin, a vinyl resin, or a resin sheet, copper, aluminum, iron, Examples thereof include metal plates such as brass, zinc, magnesium, and nickel, or resin boards or resin sheets containing metal materials, slate plates, gypsum boards, ALC plates, wood cement boards, and plywood. Such a heat conductor may cause dew condensation at night or in winter, but by laminating the latent heat storage body of the present invention, the temperature change of the heat conductor can be mitigated and condensation can be prevented. Can do.

  Further, by laminating the latent heat storage body of the present invention and a fireproofing material such as a flame retardant, a semi-incombustible material, and a noncombustible material, in addition to excellent latent heat storage properties, fireproofing can be imparted, and fireproofing This can also be applied to a part that requires the above (for example, an interior material of a building). Examples of such fireproof materials include concrete plates, glass plates, metal plates, wooden wool cement plates, plaster boards, flat plates such as calcium silicate plates, metal film, film molded products such as glass fibers, and foamable fireproof materials. And flame retardant-containing materials.

  Moreover, by laminating the latent heat storage body and the heating element of the present invention, it can be applied to, for example, a floor heating system, a snow melting / icing roof material, a bathtub / bathroom, a heat insulation sheet, and the like. When applied as a floor heating system, for example, a planar heating element, piping using hot water, or the like can be used as a heating element, and these heating elements are combined with the latent heat storage element and flooring of the present invention. Can do. Such a floor heating system can be stacked and installed by a known method. For example, a floor heating system in which a heating element, a planar heating element, and a flooring material are stacked can suppress the thickness, and Even if the thickness is suppressed, an excellent floor heating effect and an energy saving effect can be exhibited, and particularly, it can be suitably used for reforming and the like.

  Moreover, since the heat storage body of this invention can continue maintaining optimal temperature, it can obtain a comfortable environment by combining with the raw material used for a clothing, a curtain, a carpet, bedding, etc., for example.

  Furthermore, since it is possible to suppress the influence of external temperature even in extremely cold areas and high-temperature environments such as fire places, it is also effective for cold clothes and fire fighting clothes.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited only to these examples.
Further, in the present invention, unless otherwise specified, “part” is “part by mass” and “%” is “mass%”.
The measurement method and evaluation method used in the present invention are as follows.

[Evaluation of compatibility between organic latent heat storage material (A) and polyester polyol (C) and criteria for determination]
In a glass container, normal pentadecane having 15 carbon atoms as the organic latent heat storage material (A) (trademark: TS paraffin TS5, manufactured by JX Nippon Mining & Energy Corporation, melting point 10 ° C., heat of fusion (measured value) 216 J / g) The polyester polyol obtained in the synthesis example as a polyester polyol (C) is mixed and dissolved in a 50/50 mass ratio, and then the appearance is visually observed after standing at room temperature for 24 hours. Judged.
Criteria for compatibility.
○: Uniform and transparent, no turbidity.
Δ: Turbid.
X: Separated unevenly.

[Gel hardening test and gel stability test of latent heat storage material (paraffin gel)]
Evaluation (1) determination of gel curability and evaluation (2) determination of gel stability were performed using test samples of latent heat storage bodies (paraffin gel) prepared in Examples and Comparative Examples.

Evaluation (1) Judgment of Gel Curability (1-1) Appearance / Finger Touch The appearance of the test sample of the latent heat storage body (paraffin gel) obtained above is determined by visual observation and presence / absence of deposits when touched. Judgment was made according to the criteria.
Judgment criteria for gel curability ○: No bleeding or separation, and no deposit when touched.
(Triangle | delta): There exists a deposit or a deposit | sticker at the time of a finger touch.
X: Separated unevenly.

(1-2) Measurement of paraffin outflow rate (α) The initial mass (W ₀ ) of the test sample of the latent heat storage body (paraffin gel) was weighed in advance. Subsequently, the test sample of the latent heat storage body (paraffin gel) obtained above was wiped with absorbent cotton, and the paraffin separated / flowed out from the test sample was collected, and the mass (W ₁ ) of the separated / outflowed paraffin was measured. The paraffin outflow rate α (%) relative to the initial mass (W ₀ ) was calculated from the following formula.
Paraffin outflow rate α (%) = W ₁ / W ₀ × 100
α: Paraffin outflow rate (% by mass)
W ₀ : Initial mass of the latent heat storage body (paraffin gel) W ₁ : Mass of the paraffin separated and flowed out

Evaluation (2) Judgment of gel stability The test sample of the latent heat storage body (paraffin gel) obtained in Examples and Comparative Examples was allowed to stand at -10 ° C for 1 hour and then left at 50 ° C for 1 hour, and this was performed for one cycle. As a result, a 20-cycle gel stability test was conducted.
(2-1) Appearance / Finger Touch The appearance after the gel stability test was determined according to the following criteria by visual observation and presence / absence of deposits during finger touch.
Judgment criteria for gel curability ○: No bleeding or separation, and no deposit when touched.
(Triangle | delta): There exists a deposit or a deposit | sticker at the time of a finger touch.
X: Separated unevenly.

(2-2) Measurement of paraffin outflow rate (β) The initial mass (W ₀ ) of the test sample of the latent heat storage body (paraffin gel) obtained in Examples and Comparative Examples was weighed in advance. Subsequently, the test sample after performing the above-mentioned gel stability test on these test samples was wiped with absorbent cotton, and the paraffin that separated and flowed out was collected, and the mass (W ₂ ) of the separated and flowed paraffin was measured. The paraffin outflow rate β (%) relative to the initial mass (W ₀ ) was calculated from the following formula.
Paraffin outflow rate β (%) = W ₂ / W ₀ × 100
β: Paraffin outflow rate (% by mass)
W ₀ : Initial mass of the latent heat storage body (paraffin gel) W ₂ : Mass of the paraffin separated and outflowed

[Measurement method of heat of fusion]
The calorific value (unit: J / g, joule per gram) of the detected melting peak was measured by a differential scanning calorimeter (Differential Scanning Calorimeter, abbreviated as DSC).
Measuring instrument: Model: DSC Q-100, Manufacturer: TA Instruments, Inc. Measuring atmosphere: Nitrogen Measuring temperature range: -100 ° C to 100 ° C
Temperature increase rate: 10 ° C / min

[Synthesis Example 1] Synthesis of Polyester Polyol C1 In a reaction vessel, 800 parts of succinic anhydride having an alkenyl group (trademark: AS-1532, manufactured by Seiko PMC Co., Ltd., having 18 carbon atoms in the alkenyl group) 120 parts of ethylene glycol (hereinafter abbreviated as “EG”) and 80 parts of trimethylolpropane (hereinafter abbreviated as “TMP”) were charged. Furthermore, 0.005% of tetraisopropyl titanate as an esterification catalyst was added to the total charge, and 0.01% of toluhydroquinone was added as a polymerization inhibitor to the total charge. Subsequently, it was made to react at 220 degreeC for 48 hours, and polyester polyol C1 which is a pale yellow transparent liquid was obtained.

Synthesis Example 2 Synthesis of Polyester Polyol C2 In a reaction vessel, 680 parts of succinic anhydride having an alkenyl group (trademark: AS-1532, the same as above) and 290 of butylethylpropanediol (hereinafter abbreviated as “BEPD”) And 30 parts of TMP were charged. Furthermore, 0.005% of tetraisopropyl titanate as an esterification catalyst was added to the total charge, and 0.01% of toluhydroquinone was added as a polymerization inhibitor to the total charge. Subsequently, it was made to react at 220 degreeC for 48 hours, and polyester polyol C2 which is a pale yellow transparent liquid was obtained.

Synthesis Example 3 Synthesis of Polyester Polyol C3 In a reaction vessel, 800 parts of succinic anhydride having an alkenyl group (trademark: ASA-2024, manufactured by Dixie Chemical Company, alkenyl group having 20 to 24 carbon atoms), 120 parts of EG and 20 parts of TMP were charged. Furthermore, 0.005% of tetraisopropyl titanate as an esterification catalyst was added to the total charge, and 0.01% of toluhydroquinone was added as a polymerization inhibitor to the total charge. Subsequently, it was made to react at 220 degreeC for 48 hours, and polyester polyol C3 which is a pale yellow transparent liquid was obtained.

Synthesis Example 4 Synthesis of Polyester Polyol C4 In a reaction vessel, 590 parts of succinic anhydride having an alkenyl group (trademark: AS-1532, the same as above), 380 parts of 1,12-dodecanediol, and 30 parts of TMP Prepared. Furthermore, 0.005% of tetraisopropyl titanate as an esterification catalyst was added to the total charge, and 0.01% of toluhydroquinone was added as a polymerization inhibitor to the total charge. Subsequently, it was made to react at 220 degreeC for 48 hours, and polyester polyol C4 which is a pale yellow transparent liquid was obtained.

Synthesis Example 5 Synthesis of Polyester Polyol C5 In a reaction vessel, 720 parts of dimer acid (trademark: Tsunodim 227, manufactured by Tsukino Food Industries, Ltd., containing about 80% of a dicarboxylic acid having 36 carbon atoms), BEPD 70 parts and 210 parts of 1,12-dodecanediol were charged. Further, 0.01% of monobutyltin oxide as an esterification catalyst with respect to the total charged amount and 0.05% of toluhydroquinone as a polymerization inhibitor with respect to the total charged amount were added. Subsequently, it was made to react at 220 degreeC for 15 hours, and polyester polyol C5 which is a yellow transparent liquid was obtained.

Synthesis Example 6 Synthesis of Polyester Polyol C6 In a reaction vessel, 760 parts of dimer acid (trademark: Tsunodim 227, the same as above), 120 parts of BEPD, and 1,9-nonanediol / 2-methyl-1,8 -120 parts of a mixture of octanediol (trademark: ND15, manufactured by Kuraray Co., Ltd.) was charged. As an esterification catalyst, monobutyltin oxide was added in an amount of 0.01% with respect to the total charged amount, and as a polymerization inhibitor, toluhydroquinone was added in an amount of 0.05% with respect to the total charged amount. Subsequently, it was made to react at 220 degreeC for 15 hours, and polyester polyol C6 which is a yellow transparent liquid was obtained.

[Example 1]
Normal pentadecane having 15 carbon atoms as an organic latent heat storage material (A), a modified isophorone diisocyanate as a polyisocyanate (B), and a polyester polyol C1 obtained in Synthesis Example 1 as a polyester polyol (C) [NCO / OH ] = 1.00 molar ratio to prepare the latent heat storage material composition of the present invention. In addition, preparation was performed by the said method 1.
The blending ratio of the organic latent heat storage material (A) at that time was 80% by mass with respect to the total amount of the organic latent heat material (A), the polyisocyanate (B), and the polyester polyol (C). .
The latent heat storage material composition is placed in a glass container and allowed to stand for 48 hours in a constant temperature bath at an internal temperature of 50 ° C. to react and cure the polyisocyanate (B) and the polyester polyol (C), thereby the latent heat storage body of the present invention. (Paraffin gel) G1 was produced.
The evaluation results of the latent heat storage body (paraffin gel) G1 are shown in Table 1.
The latent heat storage body (paraffin gel) G1 of the present invention was excellent in appearance and exudation after the gel curing test, and was excellent in stability without appearance and exudation after the gel stability test.

[Example 2 and Example 3]
As the polyester polyol (C), the same operation as in Example 1 was carried out except that the polyester polyols C2 and C3 obtained in Synthesis Example 2 and Synthesis Example 3 were used in place of the polyester polyol C1, respectively. A material composition was prepared. The blending ratio of the organic latent heat storage material (A) at that time was 80% by mass for the (A) with respect to the total amount.
In the same manner as in Example 1, latent heat storage bodies (paraffin gels) G2 and G3 of the present invention were produced.
The evaluation results of the latent heat storage bodies (paraffin gels) G2 and G3 are shown in Table 1.
The latent heat storage bodies (paraffin gels) G2 and G3 of the present invention were excellent in appearance and exudation after the gel curing test, and were excellent in stability without appearance and exudation after the gel stability test.

[Comparative Example 1]
In the same operation as in Example 1, normal pentadecane having 15 carbon atoms as an organic latent heat storage material, isophorone diisocyanate modified as polyisocyanate, and polyester polyol C4 obtained in Synthesis Example 4 were [NCO / OH] = 1. A latent heat storage material composition was prepared by blending at a 0.000 molar ratio.
The blending ratio of the organic latent heat storage material (normal pentadecane) at that time was 80% by mass with respect to the total amount of the normal pentadecane, the isophorone diisocyanate-modified product, and the polyester polyol C4.
The latent heat storage material composition is put in a glass container and left in a constant temperature bath at an internal temperature of 50 ° C. for 48 hours to react and cure the isophorone diisocyanate-modified product and the polyester polyol C4, and the latent heat storage material (paraffin gel) G4 is obtained. Produced.
The evaluation results of the latent heat storage body (paraffin gel) G4 are shown in Table 1.
In the latent heat storage body (paraffin gel) G4, the compatibility between normal pentadecane and polyester polyol C4 was good, but separation occurred in the gel curing test, and there was an outflow of paraffin. .

[Comparative Example 2 and Comparative Example 3]
The latent heat storage material composition and the latent heat storage material (paraffin) were obtained by performing the same operation as in Example 1 except that the polyester polyols C5 and C6 obtained in Synthesis Example 5 and Synthesis Example 6 were used instead of the polyester polyol C1. Gel) G5 and G6 were prepared.
The evaluation results of the latent heat storage bodies (paraffin gels) G5 and G6 are shown in Table 1.
In the above latent heat storage bodies (paraffin gels) G5 and G6, the compatibility between normal pentadecane and polyester polyols C5 and C6 was good, but phase separation occurred in the gel curing test, and there was an outflow of paraffin. It was an unbearable result.

[Comparative Example 4]
In Comparative Example 4, the same operation as in Example 1 was performed, except that polypropylene glycol (having a number average molecular weight of 1000), which is a polyether polyol, was used instead of the polyester polyol C1. Prepared.
The organic latent heat storage material (normal paraffin) and polypropylene glycol were very poor in compatibility and phase-separated. The evaluation results are shown in Table 1.

In addition, the symbol of Table 1 means the following name.
EG: Ethylene glycol BEPD: Butylethylpropanediol 1,12-DD: 1,12-dodecanediol ND15: Mixture of 1,9-nonanediol / 2-methyl-1,8-octanediol TMP: Trimethylolpropane PPG1000: Polypropylene glycol

  According to the latent heat storage material composition of the present invention, the latent heat storage material has excellent performance such as compatibility and gel stability, which does not cause problems such as bleeding and phase separation no matter how many times the phase change between solidification and melting is repeated. You can get a body. The latent heat storage body of the present invention is useful for a wide range of applications such as heat storage floor heating and air conditioning systems, as well as various fields such as facilities, electrical and electronics, industry, housing, and transportation.

Claims (6)

An organic latent heat storage material (A), and a latent heat storage material composition comprising a polyisocyanate (B) and a polyester polyol (C) and containing a reacted thermosetting polyurethane resin,
The polyester polyol (C) is a polyester polyol synthesized from a raw material containing 60 to 90% by mass of succinic anhydride or succinic acid having an alkenyl group with respect to the total amount of the raw material. Latent heat storage material composition.   The latent heat storage material composition according to claim 1, wherein the alkenyl group is an alkenyl group having 8 to 50 carbon atoms.   The latent heat storage material composition according to claim 1, wherein the organic latent heat storage material (A) is normal paraffin.   The latent heat storage material composition according to claim 1, wherein the polyisocyanate (B) is an aliphatic polyisocyanate, an alicyclic polyisocyanate, or a modified product thereof.   The organic latent heat storage material (A) is in a range of 30 to 90% by mass with respect to the total amount of the organic latent heat storage material (A) and the charged amount of the polyisocyanate (B) and the polyester polyol (C). The latent heat storage material composition according to claim 1, which is contained.   A latent heat storage element obtained by using the latent heat storage material composition according to any one of claims 1 to 5.