JP2020193237A - Heat storage material composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat storage material composition which can easily design each predetermined temperature, maintain a high latent heat amount, and have excellent heat storage property.
The heat storage material composition of the present invention is characterized by containing two specific types of fatty acid esters.
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Description

The present invention relates to a heat storage material composition that facilitates each predetermined temperature design, maintains a high latent heat amount, and has excellent heat storage properties.

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.

Japanese Unexamined Patent Publication No. 2005-134101 Japanese Unexamined Patent Publication No. 2018-76485

Examples of the organic latent heat storage material include paraffin-based, fatty acid ester-based, fatty acid-based, fatty acid triglyceride-based, aliphatic alcohol-based, and aliphatic ether-based materials, which have a particularly large latent heat amount and are excellent in handleability. , Fatty acid ester. Such fatty acid esters have a latent heat amount and a phase change temperature peculiar to the substance.
However, it may be difficult to design in the desired temperature range or the like with only one type, and in such a case, it is possible to design by mixing two or more types of fatty acid esters.
For example, Patent Documents 1 and 2 describe a heat storage material in which two types of fatty acid esters are mixed. (See Examples)

However, when two or more kinds of fatty acid esters are mixed, the latent heat amount may be significantly reduced depending on the mixing ratio, and it may be difficult to maintain excellent heat storage performance.

As a result of diligent studies in order to solve the above problems, the present invention facilitates each predetermined temperature design and maintains a high latent heat amount by mixing two or more specific fatty acid esters as latent heat storage materials. A heat storage material composition capable of exhibiting excellent heat storage properties has been found, and the present invention has been completed.

That is, the present invention has the following features.
1. 1. A heat storage material composition containing the fatty acid ester (1) represented by the formula (1) and the fatty acid ester (2) represented by the formula (2).
(1) R ^1- C (= O) -O-R ²
(2) R ^1- C (= O) -O-R ³
(R ¹ is an alkyl group having 13 or more carbon atoms and 21 or less carbon atoms, R ² is an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms, and R ³ is an alkyl group having 4 carbon atoms).
2. 2. 1. The mixing ratio (weight ratio) of the fatty acid ester (1) and the fatty acid ester (2) is 1:99 to 99: 1. The heat storage material composition according to.

The heat storage material composition of the present invention can easily design each predetermined temperature, maintain a high latent heat amount, and can exhibit excellent heat storage properties.

It is a temperature-time graph of the heat storage test of this invention.

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

The heat storage material composition of the present invention includes a fatty acid ester (1) represented by the formula (1) (hereinafter, also referred to as “component (1)”) and a fatty acid ester (2) represented by the formula (2) (hereinafter referred to as “component”). It is characterized by containing "(2) component").
(1) R ^1- C (= O) -O-R ²
(2) R ^1- C (= O) -O-R ³
(R ¹ is an alkyl group having 13 or more carbon atoms and 21 or less carbon atoms, R ² is an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms, and R ³ is an alkyl group having 4 carbon atoms).

Examples of the component (1) of the present invention include methyl myristate (phase change temperature 18 ° C.), ethyl myristate (phase change temperature 12 ° C.), propyl myristate (phase change temperature −5 ° C.), and isopropyl myristate (phase change temperature −5 ° C.). Phase change temperature 8 ° 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 10 ° C) , Methyl stearate (phase change temperature 38 ° C), ethyl stearate (phase change temperature 36 ° C), propyl stearate (phase change temperature 29 ° C), isopropyl stearate (phase change temperature 28 ° C), methyl arachidate (phase) (Change temperature 45 ° C.), ethyl arachidate (phase change temperature 42 ° C.), and the like, and one or more of these can be used.
Examples of the component (2) of the present invention include butyl myristate (phase change temperature 7 ° C.), butyl palmitate (phase change temperature 17 ° C.), butyl stearate (phase change temperature 22 ° C.), and the like. One or more of them can be used.

As a mixture of two or more fatty acid esters, for example, when two of the components (1) are mixed, especially when the mixing ratio is around 50:50, the phase change temperature is broadened or polarized, which is desired. In the temperature range, the latent heat amount (heat storage property) decreases.
The present invention solves such a problem, and by mixing the component (1) and the component (2), it is possible to design the desired temperature according to the mixing ratio, and the temperature is high in various mixing ratios. It is possible to design a heat storage material that maintains the latent heat amount (excellent heat storage property). For example, when methyl palmitate (phase change temperature 28 ° C) is used as the component (1) and butyl stearate (phase change temperature 22 ° C) is used as the component (2), the temperature varies from about 20 ° C to 28 ° C depending on the mixing ratio. It is possible to design a heat storage material that maintains a high latent heat amount (excellent heat storage property) at a nearby temperature.

The mixing ratio in the present invention is (1) component: (2) component by weight ratio of 1:99 to 99: 1 (further, 5:95 to 95: 5, and further 10:90 to 90:10). It is preferable to have.
In the formulas (1) and (2), R ¹ is an alkyl group having 13 or more and 21 or less carbon atoms, more preferably an alkyl group having 15 or more and 19 or less carbon atoms, and is linear, branched, or saturated. Although not particularly limited such as unsaturated, in the present invention, a linear saturated alkyl group is preferable, and the alkyl groups of the formulas (1) and (2) may be the same or different.
In the formula (1), R ² is an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms, and is linear or branched. In the present invention, a linear alkyl group is preferable, and further, an alkyl having 1 carbon atom is preferable. Groups are preferred.
In the formula (2), R ³ is an alkyl group having 4 carbon atoms, and is linear or branched. In the present invention, a linear alkyl group having 4 carbon atoms is preferable.
If the carbon number of R ^{1 in} the formulas (1) and (2) is too short, the heat storage property is inferior.
If the carbon number of R ^{2 in} the formula (1) is too long, the heat storage property is inferior, and when mixed with the component (2), the latent heat amount is further reduced.
When the carbon number of R ^{3 in} the formula (2) is 1 to 3, a decrease in the latent heat amount may be observed when the component (1) and the component (2) are mixed. When the number of carbon atoms of R ³ is too long, poor heat storage, also (1) and (2) when mixing of the components, it is observed further decrease in the quantity of latent heat.

In the present invention, other heat storage materials other than the component (1) and the component (2) can be used in combination so as not to impair the effects of the present invention.
Other heat storage materials include, for example, methyl laurate (phase change temperature 5 ° C.), ethyl laurate (phase change temperature -10 ° C), propyl laurate (phase change temperature 4 ° C.), 2-ethylhexyl palmitate (phase). Fatty acid esters such as 2-ethylhexyl stearate (phase change temperature 10 ° C), myristyl myristate (phase change temperature 38 ° C), stearyl stearate (phase change temperature 60 ° 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,
Octanoic acid (phase change temperature 17 ° C), decanoic acid (phase change temperature 32 ° C), dodecanoic acid (phase change temperature 44 ° C), tetradecanoic acid (phase change temperature 50 ° C), hexadecanoic acid (phase change temperature 63 ° C), Fatty acids such as octadecanoic 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.

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 is, for example, a floor heating system, an air conditioning system, an interior material such as a vehicle, an industrial product such as a machine / equipment, a thermoelectric conversion system, a heat transfer medium, a refrigerator / freezer, a vending machine, and the like. 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 necessities, etc. ..

Examples of the method of using the heat storage material composition of the present invention include a method of encapsulating and using the heat storage material composition such as packaging and encapsulation, a method of mixing with a resin or the like and using the heat storage material composition, a method of permeating into a fiber, a porous substrate or the like. A method of using the above, a method of using these in combination, and the like can be mentioned.
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.
In the encapsulation method, for example, acrylic resin, silicon resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, vinyl acetate resin, acrylic / vinyl acetate resin. , Acrylic / urethane resin, acrylic / silicon resin, silicon-modified acrylic resin, urethane urea resin, ethylene / vinyl acetate / versatic acid vinyl ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS resin, AS resin, etc. Examples thereof include a method of injecting a heat storage material composition into a capsule having a capsule wall, and a method of mixing a monomer which is a precursor of a synthetic resin and a heat storage material composition and polymerizing them to obtain a heat storage capsule.
In the method of mixing with a resin or the like and using it as a heat storage forming body, for example, acrylic resin, silicon resin, polyester resin, alkyd resin, epoxy resin, urethane resin, phenol resin, melamine resin, amino resin, polycarbonate resin, fluororesin, acetic acid. Vinyl resin, acrylic / vinyl acetate resin, acrylic / urethane resin, acrylic / silicon resin, silicon-modified acrylic resin, urethane urea resin, ethylene / vinyl acetate / versatic acid vinyl ester resin, ethylene / vinyl acetate resin, vinyl chloride resin, ABS Examples thereof include a method in which one or more selected from synthetic resins such as resins and AS resins and precursors thereof are mixed with a heat storage material composition and cured to obtain a heat storage form.
In the method of permeating into fibers, porous substrates, etc., for example, natural fibers such as cotton, linen, 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 , Wood wool cement board, porous base material such as plywood, wood base material such as bamboo charcoal and charcoal, foamed resin base material such as urethane foam board and foamed styrene board, etc. Can be used.

The heat storage composition of the present invention can also be used by adding various additives.
Additives include, for example, layered clay minerals, surfactants, heat conductive substances, compatibilizers, reaction accelerators, flame retardants, pigments, aggregates, viscosity regulators, plasticizers, buffers, dispersants, crosslinkers. , Acidity regulators, preservatives, antifungal agents, antibacterial agents, algae repellents, wetting agents, defoamers, leveling agents, lubricants, dehydrators, UV absorbers, antioxidants, light stabilizers, fibers, fragrances , Chemical substance adsorbents, photocatalysts, moisture absorbing / releasing powders and granules, etc., and one or more of these can be used.

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

Fatty acid esters were mixed at 50 ° C. with the raw materials and blending amounts shown in Table 1 to obtain a heat storage material composition.
100 g of the obtained heat storage material composition was put into a polypropylene cup (250 ml) and allowed to stand at 50 ° C. for 3 hours in an incubator.
(Heat storage test)
In the heat storage test, a thermocouple was installed at the center of the heat storage material composition at 50 ° C. obtained by the above method so that the temperature could be measured, and the thermocouple was allowed to stand in an incubator under a 5 ° C. environment. The temperature of the heat storage material composition was measured. The evaluation was performed as follows. The evaluation results are shown in Table 1.
⊚: There was a temperature range that could be maintained for 90 minutes or more.
◯: There was a temperature range that could be maintained for 60 minutes or more.
Δ: The temperature range that can be maintained was less than 60 minutes.
X: The temperature range that can be maintained is less than 45 minutes, or the temperature drops below 15 ° C. within 60 minutes of the start of the test.
The temperature range that can be maintained in this test is a temperature range that maintains a temperature within plus or minus 0.5 ° C.

For Reference Example 2, Reference Example 4, Example 3, Comparative Example 1, Comparative Example 4, and Comparative Example 5, the temperature changes due to the heat storage test are shown in FIG.
In Reference Examples 2 and 4, the results were such that the temperature could be maintained for 90 minutes or more in the vicinity of the phase change temperature, respectively.
In Example 3, the result was that it could last for 90 minutes or more in the temperature range of 20.1 ° C.
On the other hand, in Comparative Example 1, Comparative Example 4, and Comparative Example 5, the temperature maintenance in the specific temperature zone was inferior.

Claims (2)

A heat storage material composition containing the fatty acid ester (1) represented by the formula (1) and the fatty acid ester (2) represented by the formula (2).
(1) R ^1- C (= O) -O-R ²
(2) R ^1- C (= O) -O-R ³
(R ¹ is an alkyl group having 13 or more carbon atoms and 21 or less carbon atoms, R ² is an alkyl group having 1 or more carbon atoms and 3 or less carbon atoms, and R ³ is an alkyl group having 4 carbon atoms). The heat storage material composition according to claim 1, wherein the mixing ratio (weight ratio) of the fatty acid ester (1) and the fatty acid ester (2) is 1:99 to 99: 1.

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