JP2020196799A - Heat storage material composition - Google Patents

Abstract

To provide a heat storage material composition having excellent heat storage properties and leak resistance.SOLUTION: A heat storage material composition contains (A) fatty acid ester, (B) polyol, (C) isocyanate, and (D) a hydroxy group-containing compound having one primary hydroxy group and a C8-24 alkyl segment in one molecule.SELECTED DRAWING: None

Description

The present invention relates to a heat storage material composition having excellent heat storage properties and leakage resistance.

In recent years, heat storage technology that effectively utilizes natural energy such as solar heat and geothermal heat and residual heat from heating and cooling appliances has been attracting attention as one of the technologies for solving energy problems.
As a heat storage material used in such a heat storage technology, an organic latent heat storage material that stores heat (heat storage) when a substance changes phase from solid to liquid and releases heat (dissipates) when the phase changes from liquid to solid. Has a high latent heat and is easy to handle, so research is being conducted for practical use.

JP-A-2015-81297 Japanese Unexamined Patent Publication No. 2017-137437

For example, Patent Document 1 describes a latent heat storage material composition containing an organic latent heat storage material, a polyisocyanate, and a hydrogenated polybutadiene-based polyol.
Further, Patent Document 2 describes heat storage particles having a core portion containing a heat storage substance (latent heat storage material) and a shell portion containing polyurethane polyurea.
In general, since the latent heat storage material repeatedly changes its state between a liquid and a solid, it is difficult to maintain its shape and state, and even with the methods of Patent Documents 1 and 2, it is difficult to solve the problem of leakage of the latent heat storage material.

As a result of diligent studies in order to solve the above problems, the present invention uses a fatty acid ester as a latent heat storage material, and by using a specific hydroxyl group-containing compound having one primary hydroxyl group together with a polyol and an isocyanate. It has been found that a heat storage material composition having excellent heat storage properties and excellent leakage resistance can be obtained, and the present invention has been completed.

That is, the present invention has the following features.
1. 1. (A) Fatty acid ester,
(B) polyol,
(C) Isocyanate and
(D) A heat storage material composition, which comprises one primary hydroxyl group and a hydroxyl group-containing compound having an alkyl segment having 8 or more and 24 or less carbon atoms in one molecule.

The heat storage material composition of the present invention has excellent heat storage properties and also excellent leak resistance.

Hereinafter, embodiments for carrying out the present invention will be described in detail.

The heat storage composition of the present invention includes (A) fatty acid ester (hereinafter, also referred to as "(A) component"), (B) polyol (hereinafter, also referred to as "(B) component"), and (C) isocyanate (hereinafter, "" (C) component ”) and (D) a hydroxyl group-containing compound having one primary hydroxyl group and an alkyl segment having 8 to 24 carbon atoms in one molecule (hereinafter also referred to as“ (D) component ”. ) Is contained.

The component (A) of the present invention is a fatty acid ester, which is a component used as a heat storage material.
Examples of such component (A) include methyl laurate (phase change temperature 5 ° C.), ethyl laurate (phase change temperature −10 ° C.), propyl laurate (phase change temperature 4 ° C.), and methyl myristate (phase change temperature 4 ° C.). Phase change temperature 19 ° C), ethyl myristate (phase change temperature 12 ° C), propyl myristate (phase change temperature -5 ° C), isopropyl myristate (phase change temperature 8 ° C), butyl myristate (phase change temperature 7 ° C) ), Myristyl myristate (phase change temperature 38 ° C), methyl palmitate (phase change temperature 28 ° C), ethyl palmitate (phase change temperature 25 ° C), propyl palmitate (phase change temperature 20 ° C), isopropyl palmitate (phase change temperature 20 ° C) Phase change temperature 10 ° C), butyl palmitate (phase change temperature 17 ° C), 2-ethylhexyl palmitate (phase change temperature 0 ° C), methyl stearate (phase change temperature 38 ° C), ethyl stearate (phase change temperature 36 ° C) ℃), propyl stearate (phase change temperature 29 ℃), isopropyl stearate (phase change temperature 28 ℃), butyl stearate (phase change temperature 22 ℃), 2-ethylhexyl stearate (phase change temperature 10 ℃), stearate Stearic acid esters such as stearyl acid (phase change temperature 60 ° C), methyl arachidate (phase change temperature 45 ° C), ethyl arachidate (phase change temperature 42 ° C), etc.
n-decane (phase change temperature -30 ° C), n-undecane (phase change temperature -25 ° C), n-dodecane (phase change temperature -8 ° C), n-tridecane (phase change temperature -5 ° C), pentadecane (phase change temperature -5 ° C) Phase change temperature 6 ° C), n-tetradecane (phase change temperature 8 ° C), n-hexadecan (phase change temperature 17 ° C), n-heptadecane (phase change temperature 22 ° C), n-octadecan (phase change temperature 28 ° C) , N-Nonadecan (phase change temperature 32 ° C.), icosane (phase change temperature 36 ° C.), docosane (phase change temperature 44 ° C.), etc. and n-paraffin or paraffin wax composed of a mixture thereof,
Octadecane (phase change temperature 17 ° C), decanoic acid (phase change temperature 32 ° C), dodecanoic acid (phase change temperature 44 ° C), tetradecane acid (phase change temperature 50 ° C), hexadecane acid (phase change temperature 63 ° C), Fatty acids such as octadecane acid (phase change temperature 70 ° C),
Fatty alcohols such as capryl alcohol (phase change temperature 7 ° C), lauryl alcohol (phase change temperature 24 ° C), myristyl alcohol (phase change temperature 38 ° C), stearyl alcohol (phase change temperature 58 ° C),
Etc., and one or more of these can be used.
In the present invention, in particular, methyl myristate (phase change temperature 19 ° C.), methyl palmitate (phase change temperature 30 ° C.), butyl palmitate (phase change temperature 17 ° C.), methyl stearate (phase change temperature 38 ° C.), It is preferable to use one or more selected from butyl stearate (phase change temperature 22 ° C.).

The component (B) of the present invention mainly reacts with the component (C) described later and exhibits an action of immobilizing the component (A).

As the component (B), those having two or more primary hydroxyl groups in one molecule are preferable, and for example, a polyether polyol, a polyester polyol, an acrylic polyol, a polycarbonate polyol, a polycaprolactone polyol, a polytetramethylene glycol polyol, and a polybutadiene Examples thereof include polyols, polyoxypropylene polyols, polyoxypropylene ethylene polyols, epoxy polyols, alkyd polyols, fluorine-containing polyols, silicon-containing polyols, castor oil-based polyols, cellulose and / or derivatives thereof, and polysaccharides such as amylose.

Examples of the polyether polyol include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether, as well as monomers such as ethylene oxide-propylene oxide copolymer. A copolymer containing a plurality of alkylene oxides (alkylene oxide-other alkylene oxides) as a component, and alkylene oxides (for example, at least one of ethylene oxide, propylene oxide, etc., the same shall apply hereinafter) are added using bisphenol A as an initiator. Bisphenol A type polyether polyol, aromatic amines (eg, toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, triethanolamine, etc. Aromatic amine-based polyether polyol obtained by adding alkylene oxide using Mannig condensate as an initiator, polyether polyol obtained by adding alkylene oxide using glycerin as an initiator, low molecular weight amine (for example, for example). Examples thereof include an amino group-containing polyether polyol having an alkylene oxide added as an initiator (ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, neopentyl diamine, etc.).

Examples of the polyester polyol include a condensation polymer of a polyhydric alcohol and a polyvalent carboxylic acid; a condensation polymer of a polyhydric alcohol and a hydroxycarboxylic acid; a ring-opening polymer of a cyclic ester (lactone); a polyhydric alcohol, a polyvalent Examples thereof include reactants consisting of three or more kinds of components among valent carboxylic acid, hydroxycarboxylic acid and cyclic ester.

The component (C) of the present invention is not limited as long as it has two or more isocyanate groups in one molecule, but for example, an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, an aromatic aliphatic diisocyanate, etc. And those derivatized by alohanate, biuretization, dimerization (uretidine), trimerization (isocyanurate), adductation, carbodiimide reaction, etc., mixtures thereof, and copolymers with them. Examples include a copolymer with a body. These can be used alone or in combination of two or more.

Examples of the aliphatic diisocyanate include 1,3-trimethylen diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, and 1,6-hexamethylene diisocyanate (HMDI). , 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-penta Methylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanis methyl caproate, lysine diisosiane G, diisocyanate dimerate, norbornen diisocyanate and the like.

Examples of the alicyclic diisocyanate include 1,3-cyclopentane diisocyanate, 1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate, 3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate, and 4,4'. -Methylenebis (cyclohexylisocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, isophorone diisocyanate ( IPDI), norbornan diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate and the like.

Examples of the aromatic diisocyanis include m-phenylenediocyanate, p-phenylenediocyanide, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate (TDI), naphthylene-1,4-diisocyanate, and naphthylene-. 1,5-Diisocyanis, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4 , 4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisosinate, 4,4'-diphenylpropane diisocyanate, 3,3'- Examples thereof include dimethoxydiphenyl-4,4'-diisocyanis, dianisidine diisocyanate, and tetramethylene xylylene diisocyanate.

Examples of the aromatic aliphatic diisocyanate include 1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3. Examples thereof include −bis (1-isocyanate-1-methylethyl) benzene, 1,4-bis (1-isocyanate-1-methylethyl) benzene, and 1,3-bis (α, α-dimethylisocyanate methyl) benzene. ..

In the present invention, it is particularly preferable to use an aliphatic diisocyanate such as HMDI and its derivative, and an aromatic diisocyanate such as MDI and its derivative. Such an isocyanate compound is preferable because it is easy to adjust the pot life and the curing rate.

The component (D) of the present invention exhibits an action of enhancing the immobilization of the component (A) by interacting with the component (A) and partially reacting with the component (C).
The component (D) is a hydroxyl group-containing compound having one primary hydroxyl group and an alkyl segment having 8 or more and 24 or less carbon atoms in one molecule, in addition to these, having a secondary hydroxyl group, a tertiary hydroxyl group, or the like. You may.
Examples of such component (D) include 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-. Hexadecanol, 1-heptadecanol, 1-octadecanol, 1-nonadecanol, 1-icosanol, 1-docosanol, 1-tetracosanol, or 1,2-octanediol, 2-ethyl-1,3 Examples thereof include −hexanediol, 1,2-decanediol, 1,2-dodecanediol, 1,12-octadecanediol and the like, or polycondensates thereof, and one or more of these can be used.
Further, a reaction product of the above compound and a diol having two primary hydroxyl groups in one molecule or a polycondensate thereof, and a hydroxycarboxylic acid having a primary hydroxyl group in one molecule or a polycondensate thereof. Reaction product A product of a diol having two primary hydroxyl groups in one molecule or a polycondensate thereof and a carboxylic acid having no primary hydroxyl group or a polycondensate thereof, and two primary hydroxyl groups in one molecule. A monoester compound of a diol having a hydroxyl group or a polycondensate thereof or a diester compound of a triol having three primary hydroxyl groups in one molecule or a polycondensate thereof, a triol triol having four primary hydroxyl groups in one molecule Ester compounds or polycondensates thereof, pentaol tetraester compounds having 5 primary hydroxyl groups in one molecule or polycondensates thereof, hexaol pentaester compounds having 6 primary hydroxyl groups in 1 molecule, etc. (D) Included in the component.

Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 2-methyl-1,3-trimethylenediol. , Cyclohexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1 , 3-Propanediol, 2-Butyl-2-ethyl-1,3-Propanediol, 2-Methyl-1,4-Butanediol, 1,8-octanediol, 2-Methyl-1,8-octanediol, 1,9-Nonandiol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, Examples thereof include 1,18-octadecanediol and 1,20-eicosanediol, and one or more of these can be used.
Examples of the hydroxycarboxylic acid having a primary hydroxyl group include glyceric acid, 3-hydroxypropionic acid, 5-hydroxypentanoic acid, 6-hydroxyhexanoic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, and 9-hydroxynonane. Acids, 10-hydroxydecanoic acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, 15-hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 19-hydroxynonadecanic acid, 22-hydroxydocosanoic acid, mevalonic acid, pantoin Examples thereof include acids and the like, and polycondensates thereof and the like, and one or more of these can be used.
Examples of the carboxylic acid having no primary fatty acid include butanoic acid, pentanoic acid, caproic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid and heptadecanoic acid. Octadecylic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, 2-hydroxybutanoic acid, 2-hydroxypentanoic acid, 3-hydroxypentanoic acid, 3-hydroxycaproic acid, 2-hydroxyheptanic acid, 3-hydroxyheptanic acid, 2- Hydroxyoctanoic acid, 3-hydroxyoctanoic acid, 4-hydroxynonanic acid, 3-hydroxydecanoic acid, 3-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 6-hydroxytetradecanoic acid, 2-hydroxy Pentadecylic acid, 10-hydroxyhexadecanoic acid, 11-hydroxyheptadecanoic acid, 10-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 10-hydroxynonadecanic acid, 2-hydroxyicosanoic acid, 2-hydroxytetradocosanoic acid, Examples thereof include ricinoleic acid, ricineraidic acid, cerebronic acid, leucic acid, salicylic acid, castor oil fatty acid, dehydrated castor oil fatty acid, and one or more of these can be used.
Examples of triol, tetraol, pentaol, and hexaol include glycerin, trimethylolethane, trimethylolpropane, hexanetriol, sorbitol, sorbitol, pentaerythritol, dipentaerythritol, mannitol, and the like, and one of them. Or two or more types can be used.
The molecular weight (number average molecular weight) of the component (D) is not particularly limited, but is preferably 1500 or more and 5000 or less, and more preferably 2000 or more and 4000 or less.

The mixing ratio of the heat storage material composition of the present invention is such that the component (A) is preferably 30% by weight or more with respect to the total amount of the components (A), (B), (C) and (D). It is preferably 35 to 95% by weight, more preferably 40 to 90% by weight.
Further, the molar ratio (NCO / OH molar ratio) of the total hydroxyl group of the component (B) and the component (D) and the isocyanate group of the component (C) is 0.5 to 8.0 (more preferably 0.7 to 0.7). It is preferable to mix in the range of 7.0, more preferably 0.8 to 5.0). Further, the mixing ratio of the component (B) and the component (D) is preferably 90:10 to 10:90 in terms of weight ratio.

In addition to the above components, the heat storage material composition of the present invention includes, for example, layered clay minerals, surfactants, heat conductive substances, compatibilizers, reaction accelerators, flame retardants, pigments, aggregates, viscosity regulators, and plasticizers. , Buffering agents, dispersants, cross-linking agents, pH adjusters, preservatives, fungicides, antibacterial agents, algae-proofing agents, wetting agents, defoamers, leveling agents, lubricants, dehydrating agents, UV absorbers, antioxidants It can also contain additives such as light stabilizers, fibers, fragrances, chemical substance adsorbents, photocatalysts, and moisture-absorbing powders.

The heat storage material composition of the present invention can be suitably used mainly as a material for interior / exterior materials such as wall materials, ceiling materials, floor materials, and partition materials for buildings such as houses.
Further, the heat storage material composition of the present invention includes, for example, floor heating systems, air conditioning systems, interior materials such as vehicles, industrial products such as machines / equipment, thermoelectric conversion systems, heat transfer media, refrigerators / freezers, vending machines, etc. It can also be applied as a material used for baths / bathrooms, greenhouses, soil, cooler boxes, heat insulation sheets, dew condensation prevention sheets, cooling sheets, electrical products, OA equipment, plants, tanks, clothing, curtains, carpets, bedding, daily miscellaneous goods, etc. ..

Examples of the method of using the heat storage material composition of the present invention include a method of encapsulating the heat storage material composition such as packaging and encapsulation, a method of using the heat storage material composition, a method of permeating into a fiber, a porous base material, or the like, or these. Examples thereof include a method of using them in combination.
In the packaging method, for example, one or more selected from organic materials such as polyethylene, polypropylene, nylon, polyester, polyethylene terephthalate, vinylidene chloride, ethylene / vinyl acetate copolymer, etc., aluminum, gold, silver, One or more metals selected from copper, iron, chromium, zinc, magnesium, titanium, nickel, bismuth, tin, cobalt, etc., or oxides, chlorides, sulfides, carbonates, silicates, phosphoric acids of these metals It can be packaged in a film, board, box or the like containing one or more selected from salts, nitrates, sulfates and the like and composites thereof as main components.
Examples of the method used as the heat storage forming body include a method in which the component (A), the component (B), the component (C), and the component (D) are mixed and reaction-cured. The shape of such a heat storage forming body is not particularly limited, for example, a sheet shape, a rod shape, a needle shape, a spherical shape, a square shape, a powder shape, etc., and is easy to use for various purposes.
In the method of permeating into fibers, porous substrates, etc., for example, natural fibers such as cotton, hemp, wool, silk, and organic fibers such as nylon, tetron, acrylic, polyester, polyurethane, vinylon, rayon, aramid, and azole. , Woven / non-woven fabrics such as inorganic fibers such as glass, paper base materials such as paper and cardboard, fibrous base materials such as MDF, insulation board, particle board, slate board, gypsum board, ALC board, calcium silicate board , A porous base material such as wood wool cement board and plywood, a wood base material such as bamboo charcoal and charcoal, and a base material such as a foamed resin base material such as urethane foam board and foamed styrene board are impregnated with the heat storage material composition. Can be used.

Examples are shown below to clarify the features of the present invention.

Using the raw materials shown in Table 1, the fatty acid ester, the hydroxyl group-containing compound, the polyol, and the catalyst were mixed at a temperature of 50 ° C. in the blending amounts shown in Table 2, and the mixture was mixed and stirred. Further, isocyanate was added and stirred, and then 70 g was poured into a 160 mm × 109 mm × 27 mm aluminum standard vat and cured at 60 ° C. for 5 hours to obtain a test piece.
(Leakage evaluation test)
The obtained test piece was allowed to stand for 3 hours in an atmosphere of 5 ° C., and then allowed to stand for 5 hours in an atmosphere of 30 ° C. as one cycle, and the heat storage material from the test piece was subjected to 10 cycles. The leak was observed. The evaluation is as follows. The results are shown in Table 2.
⊚: No leak was observed ○: Almost no leak was observed ×: Leakage was observed

Claims (1)

(A) Fatty acid ester,
(B) polyol,
(C) Isocyanate and
(D) A hydroxyl group-containing compound having one primary hydroxyl group and an alkyl segment having 8 or more and 24 or less carbon atoms in one molecule.
A heat storage material composition characterized by containing.