CN116457439A - Heat storage material, heat storage material composition, and heat storage molded body - Google Patents

Abstract

The present invention provides a heat storage material, a heat storage material composition, and a heat storage molding. The heat storage material can contribute to exerting excellent heat storage performance, diffusion resistance, and hydrolysis resistance. The heat storage material composition contains The heat storage material is excellent in curability even when the content of the heat storage material is high, and a heat storage molded body having a high latent heat per unit volume of the molded body and excellent heat storage properties can be obtained. Even when the molded body is exposed to a high-temperature environment, the thermal storage material is less likely to dissipate and leak from the inside, and has excellent diffusion resistance and leakage resistance. The present invention relates to a heat storage material characterized by containing a saturated aliphatic monocarboxylic acid having a linear alkyl group having 8 to 20 carbon atoms and a monocarboxylic acid having 8 to 20 carbon atoms. A saturated fatty acid monoester (A) obtained by reacting a straight-chain alkyl saturated aliphatic monohydric alcohol.

Description

Heat storage material, heat storage material composition, and heat storage molded body

technical field

The present invention relates to a heat storage material excellent in heat storage properties, etc., a heat storage material composition, and a heat storage molded article obtained from the heat storage material composition.

Background technique

In recent years, heat storage technology that effectively utilizes natural energy such as solar energy and geothermal energy or waste heat from heating and cooling equipment has attracted attention as one of the technologies for solving energy problems.

As heat storage materials used in such heat storage technologies, in particular, organic latent heat storage materials that store heat (heat storage) when a substance changes phase from solid to liquid, and release heat (heat release) when a substance changes phase from liquid to solid. It has a high latent heat and is easy to handle, so it is being researched toward practical use.

In particular, in recent years, various attempts have been made to further improve heat storage properties.

As such an organic latent heat storage material, for example, Patent Document 1 discloses a heat storage body using an organic latent heat storage material such as methyl stearate or methyl palmitate, and Patent Document 2 discloses a heat storage body using an organic latent heat storage material such as methyl stearate or methyl palmitate. The fatty acid ester with a total carbon number of 23 or less and the fatty acid ester with a total carbon number of 20 or more are used as heat storage microcapsules of an organic latent heat storage material.

However, in the case of the heat storage body using the organic latent heat storage material of Patent Document 1, if the blending ratio of the heat storage material was increased, it was confirmed that the heat storage performance was improved, but on the other hand, when exposed to In a high-temperature environment, diffusion resistance and leakage resistance tend to decrease, and it is difficult to improve heat storage and diffusion resistance at the same time.

In addition, in the case of the thermal storage microcapsules of Patent Document 2, it was confirmed that the diffusion resistance and the leakage resistance were improved by encapsulation, but if the blending ratio of the thermal storage material was increased, there might be a problem in the production of the thermal storage microcapsules. When using a hot body, etc., there will be a problem in curability.

When a fatty acid ester as described above is used as an organic latent heat storage material, there is a difference between the temperature (melting point) when it changes phase from solid to liquid and the temperature (freezing point) when it changes phase from liquid to solid, There is a problem in that there is a difference in the temperature region in which the heat storage property is exhibited when the temperature changes from low temperature to high temperature and when the temperature changes from high temperature to low temperature.

In addition, although latent heat storage materials are expected to be used as building materials such as houses or transportation materials such as food and medicine, in actual use, they may be exposed to high-temperature environments or contact with water. In this case, there may be problems such as a decrease in diffusion resistance or a decrease in thermal storage performance due to hydrolysis, and further improvement in performance is desired.

prior art literature

patent documents

Patent Document 1: JP 2011-208121

Patent Document 2: Japanese Patent Laid-Open No. 2018-76485

Contents of the invention

The technical problem to be solved in the present invention

Therefore, the technical problem to be solved by the present invention is to provide a heat storage material, a heat storage material composition, and a heat storage molded body, wherein the heat storage material is helpful for exerting heat storage properties, and in particular can make the melting point and freezing point Similar to and even for any temperature change from high temperature to low temperature or from low temperature to high temperature, it can also exert excellent thermal storage performance, diffusion resistance and hydrolysis resistance at the desired set temperature; the thermal storage material composition Containing the heat storage material and having excellent curability even when the content of the heat storage material is large, a heat storage molded body having a high latent heat per unit volume of the molded body and excellent heat storage properties can be obtained; the heat storage molding Even when the body is exposed to a high temperature environment, the heat storage material is not easy to diffuse and leak from the inside, and has excellent diffusion resistance and leakage resistance.

Technical means to solve technical problems

In order to solve the above-mentioned technical problems, the present invention has conducted intensive studies, and as a result, it has been found that by using a thermal storage material (organic latent heat storage material) containing a saturated fatty acid monoester of a specific structure, it is possible to obtain a A heat storage material with diffusibility and hydrolysis resistance; and it is possible to obtain the heat storage material containing the heat storage material and even when the heat storage material is contained in a large proportion, it is also excellent in curability, and a high latent heat per unit volume of the molded body can be obtained. A thermal storage material composition of a thermal storage molded body with excellent thermal properties; and even when exposed to a high temperature environment, the thermal storage material is not easy to diffuse and leak from the inside, and a thermal storage molding with excellent diffusion resistance and leakage resistance can be obtained body, and then completed the present invention.

That is, the present invention relates to a heat storage material characterized in that it contains a saturated aliphatic monocarboxylic acid having a linear alkyl group having 8 to 20 carbon atoms and a monocarboxylic acid having a linear alkyl group having 8 to 20 carbon atoms. Saturated fatty acid monoester (A) obtained by reacting the following linear alkyl saturated aliphatic monoalcohol.

In the heat storage material of the present invention, it is preferable that the saturated fatty acid monoester (A) contains a saturated aliphatic monocarboxylic acid (a-c) having a linear alkyl group with a carbon number (Nc) of 8 or more and 20 or less. Saturated fatty acid monoester (A-1) obtained by reacting with a saturated aliphatic monohydric alcohol (a-a) having a linear alkyl group having a carbon number (Na) of 8 to 20 and satisfying the following formula (1) .

(1) (Nc)＜(Na)

In the heat storage material of the present invention, preferably: the saturated fatty acid monoester (A-1) satisfies the following formula (2).

(2) 22≤(Nc+Na)≤32

In the thermal storage material of the present invention, preferably, the saturated fatty acid monoester (A-1) satisfies the following formula (3).

(3) 4≤(Na-Nc)≤8

The present invention relates to a thermal storage material composition characterized by comprising the thermal storage material, polyol (B) and isocyanate (C).

In the thermal storage material composition of the present invention, it is preferable that the polyol (B) contains polyester polyol (B-1) and polyether polyol (B-2).

In the thermal storage material composition of the present invention, it is preferable that the content ratio of the thermal storage material in the total thermal storage material composition is 50% by mass or more and 95% by mass or less.

In the thermal storage material composition of the present invention, it is preferable that the component (B-1) contains a polyester polyol having a number average molecular weight of 1,000 to 4,000 and a number of functional groups of 2 to less than 3.

In the thermal storage material composition of the present invention, it is preferable that the component (B-2) contains a polyether polyol having a number average molecular weight of 1,000 to 12,000 and a functional group number of 2 to 3.

In the thermal storage material composition of the present invention, it is preferable that the component (C) contains a trimer of isocyanate.

In the thermal storage material composition of the present invention, it is preferable that the mixing ratio of the total amount of the component (B-1) and the component (B-2) to the component (C) is 0.75 or more in terms of NCO/OH ratio. And below 2.2.

The present invention relates to a thermal storage molded body, which is characterized in that it is formed from the thermal storage material composition.

Invention effect

The heat storage material of the present invention contributes to exhibiting excellent heat storage performance, can make the melting point and freezing point close, and can maintain the temperature at a desired set temperature even for any temperature change from high temperature to low temperature or from low temperature to high temperature. It is useful for exerting excellent heat storage properties, diffusion resistance, and hydrolysis resistance. In particular, by using the thermal storage material composition containing the thermal storage material, the obtained thermal storage molded article has excellent curability even when the content ratio of the thermal storage material is large, and the latent heat per unit volume of the molded article is high. , excellent thermal storage properties. Furthermore, even when the heat storage molded body is exposed to a high temperature environment, the heat storage material is less likely to diffuse and leak from the inside, and is excellent in diffusion resistance and leakage resistance, which is very useful.

Detailed ways

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

(heat storage material)

(A) Ingredients

The present invention relates to a heat storage material characterized by containing a saturated aliphatic monocarboxylic acid having a linear alkyl group having 8 to 20 carbon atoms and a monocarboxylic acid having 8 to 20 carbon atoms. Saturated fatty acid monoester (A) ((A) component) obtained by reacting the saturated aliphatic monohydric alcohol of linear alkyl. The component (A) functions as a heat storage material, has excellent heat storage properties, is difficult to diffuse even when exposed to a high-temperature environment, has excellent diffusion resistance, and can contribute to the development of hydrolysis resistance. Excellent heat storage performance can be exhibited at a desired set temperature even against any temperature change from high temperature to low temperature or from low temperature to high temperature. Furthermore, it is difficult to leak from the thermal storage molded body formed of the thermal storage material composition, and it is also excellent in leakage resistance.

(A-1) Ingredients

Preferably, the component (A) contains a saturated aliphatic monocarboxylic acid (a-c) having a linear alkyl group having a carbon number (Nc) of 8 to 20 and a carbon number (Na) of 8 Saturated fatty acid monoester (A-1) ((A-1) component) obtained by reacting the saturated aliphatic monohydric alcohol (a-a) of linear alkyl of 20 or more and 20 or less and satisfying following formula (1). The above-mentioned (A-1) component satisfies the following formula (1), which is excellent in heat storage and diffusion resistance, and can exhibit more excellent hydrolysis resistance. One temperature change is also preferable because it can exhibit more excellent heat storage performance at a desired set temperature. In addition, the component (A-1) is less likely to leak from the thermal storage molded body formed of the thermal storage material composition, and is also excellent in leakage resistance.

(1) (Nc)＜(Na)

The heat storage material of the present invention can make the above-mentioned The melting point of the component (A-1) is close to the freezing point, and it is useful to exhibit excellent heat storage performance at a desired set temperature even against any temperature change from high temperature to low temperature or from low temperature to high temperature. In addition, the (A-1) component can be adjusted to a desired temperature by combining the (a-c) component with a specific structure and the (a-a) component, for example, it can be adjusted to a desired temperature in a very small range (pinpoint). Temperature exerts excellent heat storage properties and is useful. In addition, the component (A-1) does not easily diffuse even when exposed to a high-temperature environment, and is excellent in diffusion resistance, and is also excellent in hydrolysis resistance even in the presence of water. In addition, the "desired temperature" is not particularly limited and can be adjusted, for example, it can be set to a temperature range of 10°C to 40°C, or can be set to a lower temperature range including sub-freezing temperature.

The difference between the melting point and the freezing point of the component (A-1) is preferably less than 2.5°C, more preferably less than 2.0°C, and still more preferably less than 1.0°C. By making the difference smaller than 2.5°C, it is possible to have excellent heat storage performance at a desired set temperature even against any temperature change from high temperature to low temperature or from low temperature to high temperature, which is preferable.

The component (A-1) preferably satisfies the above formula (1) and the following formula (2). When the component (A-1) satisfies the following formula (2), if the total number of carbon atoms (Nc+Na) is within the above range, the heat storage property and diffusion resistance are more excellent, and further Excellent hydrolysis resistance can be exhibited, and even for any temperature change from high temperature to low temperature from low temperature to high temperature, more excellent thermal storage performance can be exhibited at a desired set temperature. ) component and (B-2) component have excellent compatibility, excellent formability and curability when forming a heat storage molded body, easy to hold or hold inside a heat storage molded body, diffusion resistance, leakage resistance, and heat storage prevention Since material transferability is more excellent, it is preferable.

(2) 22≤(Nc+Na)≤32

In addition, the melting point, freezing point, phase transition temperature, and latent heat of saturated fatty acid monoesters such as the component (A-1) can be measured using a differential scanning calorimeter (DSC7000X manufactured by Hitachi High-Tech Science Corporation. .

In addition, as measurement conditions, the melting point (°C), freezing point (°C), solidification latent heat (J/g) and melting latent heat ( J/g) was measured. Phase transition temperature is the average value of freezing point (°C) and melting point (°C), and latent heat is the average value of solidification latent heat (J/g) and melting latent heat (J/g).

The component (A-1) preferably satisfies the above formula (1) and the following formula (3). The above-mentioned (A-1) component satisfies the following formula (3), so that the melting point and the freezing point can be brought closer to each other, thereby exhibiting more excellent heat storage performance at a desired set temperature and improving hydrolysis resistance ,is useful.

(3) 4≤(Na-Nc)≤8

In addition, the (A-1) component preferably has the number of carbon atoms (Nc) of 8 to 16 and the number of carbon atoms (Na) of 12 to 20, and more preferably satisfies the following: In addition to the formula (1), it satisfies the following formula (2') and/or, the following formula (3), and it is more preferable to satisfy the following formulas (1), (2') and (3) at the same time. By satisfying the conditions of the following formula, more excellent heat storage properties can be exhibited at a desired set temperature. In particular, by satisfying the following formula (2'), more excellent diffusion resistance, leakage resistance, and thermal storage material migration prevention can be exhibited, and by satisfying the following formula (3), the melting point and the freezing point can be brought closer, and It is useful to be able to improve hydrolysis resistance.

(1) (Nc)＜(Na)

(2')24≤(Nc+Na)≤30

(3) 4≤(Na-Nc)≤8

The content of the component (A-1) is preferably greater than 10% by mass, more preferably greater than 30% by mass, still more preferably greater than 50% by mass, and particularly preferably Contains more than 70% by mass. Moreover, as an upper limit, 100 mass % is preferable. By making the (A-1) component in the heat storage material more than 10% by mass, the difference between the melting point and the freezing point can be reduced as a heat storage material or a heat storage material composition containing the (A-1) component. Since it is suppressed small and heat storage property becomes excellent, it is preferable.

(A-2) Ingredients

In the heat storage material of the present invention, it is preferable that the saturated fatty acid monoester (A) contains a saturated aliphatic monocarboxylic acid (a-c) having a linear alkyl group with a carbon number (Nc) of 8 or more and 20 or less ) and a saturated aliphatic monohydric alcohol (a-a) having a straight-chain alkyl group with a carbon number (Na) of 8 or more and 20 or less is obtained by reacting a saturated fatty acid monoester (A-2) that satisfies the following formula (4) ) ((A-2) ingredient). When the above-mentioned (A-2) component satisfies the following formula (4), it is excellent in heat storage property and diffusion resistance, which is preferable. In addition, by further satisfying the following formula (4') as the above-mentioned (A-2) component, the above-mentioned effect can be further exerted, which is a more preferable aspect.

(4) (Nc)≥(Na)

(4')(Nc)＞(Na)

It is preferable that the above-mentioned (A-2) component satisfies the above formula (4) and the following formula (2). When the above-mentioned (A-2) component satisfies the following formula (2), it is more excellent in heat storage property and diffusion resistance, which is preferable.

(2) 22≤(Nc+Na)≤32

In the thermal storage material composition of the present invention, only one type of (A) component may be used as the thermal storage material, or two or more types of (A) components may be used in combination. When two or more kinds of the above-mentioned (A) components are mixed and used, it is easy to adjust the temperature setting in the temperature range which is difficult to adjust only with one kind of the above-mentioned (A) components, which is useful.

In addition, in the present invention, it is preferable to use two or more kinds of the above-mentioned (A-1) components in combination with respect to only one kind of the above-mentioned (A-1) components, or to mix and use all the above-mentioned (A-1) components. The above-mentioned (A-2) component makes it easy to set a desired temperature, adjusts the difference between the melting point and the freezing point, and can exhibit excellent heat storage properties at a desired set temperature.

In addition, when the (A-2) component is used in combination with the (A-1) component, the mixing ratio (molar ratio) of the (A-1) component to the (A-2) is In the case of [(A-1):(A-2)]=[p:q], it is preferable to satisfy both the following formula (1) and the following formula (5). By satisfying the following formula (5), when the temperature is adjusted at a desired temperature setting, the melting point and the freezing point can be brought close to each other, which is useful because of excellent hydrolysis resistance.

(1) (Nc)＜(Na)

(5) {(Nc)×[p/(p+q)] of (A-1) component + (Nc)×[q/(p+q)] of (A-2) component}<{(A -1)(Na)×[p/(p+q)] of the component +(A-2)(Na)×[q/(p+q)]} of the component

The above-mentioned (A-2) component preferably satisfies at least one kind selected from the following formula (2') in addition to satisfying the formula (4), and further satisfies two or more kinds. By satisfying the following formula, it is easy to set a desired temperature, and as the heat storage material composition, the difference between the melting point and the solidification point can be suppressed, and excellent heat storage properties can be exhibited at a desired set temperature.

(2')24≤(Nc+Na)≤30

(a-c) ingredients

The component (a-c) is a saturated aliphatic monocarboxylic acid having a linear alkyl group having a carbon number (Nc) of 8 to 20, preferably a monocarboxylic acid having a carbon number (Nc) of 8 to 16. The saturated aliphatic monocarboxylic acid having a linear alkyl group is more preferably a saturated aliphatic monocarboxylic acid having a linear alkyl group having 10 to 14 carbon atoms (Nc).

Examples of the (a-c) component include n-octanoic acid, n-nonanoic acid, n-decanoic acid, n-undecanoic acid, n-dodecanoic acid, n-tridecanoic acid, n-tetradecanoic acid, n-pentadecanoic acid, and n-pentadecanoic acid. Alkanoic acid, n-hexadecanoic acid, n-heptadecanoic acid, n-octadecanoic acid, n-nonadecanoic acid, n-eicosanoic acid, and the like can be used alone or in combination of two or more.

(a-a) ingredients

The component (a-a) is a saturated aliphatic monohydric alcohol having a straight-chain alkyl group with a carbon number (Na) of 8 to 20, preferably a straight-chain alkyl group with a carbon number (Na) of 10 to 20. The chain alkyl saturated aliphatic monohydric alcohol is more preferably a saturated aliphatic monohydric alcohol having a straight chain alkyl group having 10 to 18 carbon atoms (Na).

Examples of the (a-a) component include 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1- Myristyl alcohol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-stearyl alcohol, 1-nonadecanol, 1-eicosanol, etc., can be used 1 or more of these.

The total number of carbon atoms (Nc) of the linear alkyl group of the component (a-c) and the number of carbon atoms (Na) of the linear alkyl group of the component (a-a) is preferably 20 or more and 32 or less, More preferably, it is 22 or more and 32 or less, and it is still more preferable that it is 24 or more and 32 or less. When the total number of carbon atoms (Nc+Na) is within the above range, heat storage properties and diffusion resistance are excellent, and in addition, the components (B-1) and (B-2) components described later are It is excellent in compatibility, excellent in formability and curability when forming a thermal storage molded body, easy to hold or hold inside the molded body, and more excellent in diffusion resistance and leakage resistance, so it is preferable.

Examples of the component (A-1) include nonyl caprylate, decyl caprylate, undecyl caprylate, dodecyl caprylate, tridecyl caprylate, tetradecyl caprylate, Pentadecyl Caprylate, Cetyl Caprylate, Heptadecyl Caprylate, Octadecyl Caprylate, Nonadecyl Caprylate, Eicosyl Caprylate,

Decyl Nonanoate, Undecyl Nonanoate, Dodecyl Nonanoate, Tridecyl Nonanoate, Myristyl Nonanoate, Pentadecyl Nonanoate, Hexadecyl Nonanoate nonadecyl nonanoate, heptadecyl nonanoate, octadecyl nonanoate, nonadecyl nonanoate, eicosyl nonanoate,

Undecyl caprate, Lauryl caprate, Tridecyl caprate, Myristyl caprate, Pentadecyl caprate, Cetyl caprate, Capric acid Heptadecyl, octadecyl caprate, nonadecyl caprate, eicosyl caprate,

Lauryl Undecyl, Tridecyl Undecyl, Myristyl Undecyl, Pentadecyl Undecyl, Cetyl Undecyl, Heptadecyl Undecanoate, Octadecyl Undecanoate, Nonadecyl Undecanoate, Eicosyl Undecanoate,

Tridecyl Laurate, Myristyl Laurate, Pentadecyl Laurate, Hexadecyl Laurate, Heptadecyl Laurate, Octadecyl Laurate, Nonadecyl Laurate, Eicosyl Laurate,

Myristyl Tridecyl, Pentadecyl Tridecyl, Hexadecyl Tridecyl, Heptadecyl Tridecyl, Octadecyl Tridecyl, Nonadecyl Tridecanoate, Eicosyl Tridecanoate,

Pentadecyl Myristate, Cetyl Myristate, Heptadecyl Myristate, Octadecyl Myristate, Nonadecyl Myristate, eicosyl myristate,

Cetyl Pentadecyl, Heptadecyl Pentadecyl, Octadecyl Pentadecyl, Nonadecyl Pentadecyl, Eicosyl Pentadecyl,

Heptadecyl Cetate, Octadecyl Cetate, Nonadecyl Cetate, Eicosyl Cetate,

Octadecyl heptadecanoate, nonadecyl heptadecanoate, eicosyl heptadecanoate, nonadecyl octadecanoate, eicosyl octadecanoate,

Eicosyl nonadecanoate, etc.,

Among these, 1 type or 2 or more types of these can be used.

Examples of the component (A-2) include

Octanoate,

Octyl Nonanoate, Nonyl Nonanoate,

Octyl caprate, nonyl caprate, decyl caprate,

Octyl Undecanoate, Nonyl Undecanoate, Decyl Undecanoate, Undecyl Undecanoate,

Octyl dodecanoate, nonyl dodecanoate, decyl dodecanoate, undecyl dodecanoate, dodecyl dodecanoate,

Octyl Tridecyl, Nonyl Tridecyl, Decyl Tridecyl, Undecyl Tridecyl, Dodecyl Tridecyl, Tridecyl Tridecyl,

Octyl myristate, nonyl myristate, decyl myristate, undecyl myristate, dodecyl myristate, tridecyl myristate, Myristyl Myristate, Octyl Pentadecanoate, Nonyl Pentadecanoate, Decyl Pentadecanoate, Undecyl Pentadecanoate, Dodecyl Pentadecanoate, Tridecyl Pentadecanoate, Myristyl Pentadecanoate, Pentadecyl Pentadecanoate,

Octyl Cetate, Nonyl Cetate, Decyl Cetate, Undecyl Cetate, Dodecyl Cetate, Tridecyl Cetate, Myristyl Cetyl Cetate, Pentadecyl Cetyl Cetate, Cetyl Cetyl Cetate,

Octyl heptadecanoate, nonyl heptadecanoate, decyl heptadecanoate, undecyl heptadecanoate, dodecyl heptadecanoate, tridecyl heptadecanoate, Myristyl heptadecanoate, pentadecyl heptadecanoate, hexadecyl heptadecanoate, heptadecyl heptadecanoate,

octyl octadecanoate, nonyl octadecanoate, decyl octadecanoate, undecyl octadecanoate, dodecyl octadecanoate, tridecyl octadecanoate, Myristyl octadecanoate, pentadecyl octadecanoate, hexadecyl octadecanoate, heptadecyl octadecanoate, octadecyl octadecanoate,

Octyl nonadecanoate, Nonyl nonadecanoate, Decyl nonadecanoate, Undecyl nonadecanoate, Dodecyl nonadecanoate, Tridecyl nonadecanoate, Myristyl nonadecanoate, Pentadecyl nonadecanoate, Cetyl nonadecanoate, Heptadecyl nonadecanoate, Octadecyl nonadecanoate, nonadecanyl nonadecanoate,

Octyl Eicosanoate, Nonyl Eicosanoate, Decyl Eicosanoate, Undecyl Eicosanoate, Dodecyl Eicosanoate, Tridecyl Eicosanoate, Myristyl Eicosanoate, Pentadecyl Eicosanoate, Hexadecyl Eicosanoate, Heptadecyl Eicosanoate, Octadecyl Eicosanoate, Nonadecyl dodecanoate, eicosyl eicosanoate, etc., among these, 1 type or 2 or more types of these can be used.

The said (A) component can be produced by normal esterification reaction and transesterification reaction. In addition, after esterification, if necessary, in order to remove unreacted saturated aliphatic monocarboxylic acid or saturated aliphatic monohydric alcohol, etc., vacuum distillation, alkali neutralization and water washing treatment may be carried out. Known purification methods such as adsorption treatment of an adsorbent or evaporation (steaming).

From the viewpoint of heat storage, the lower limit of the latent heat of the (A) component (monomer) is preferably 120 J/g or more, more preferably 150 J/g or more, and the (A) component (monomer) The upper limit of the latent heat of body) is preferably 260 J/g or less, more preferably 250 J/g or less.

From the viewpoint of hydrolysis resistance, the acid value of the component (A) (monomer) is preferably 1 mgKOH/g or less, more preferably 0.5 mgKOH/g or less, even more preferably 0.1 mgKOH/g or less.

The hydroxyl value of the component (A) (monomer) is preferably 2 mgKOH/g or less, more preferably 1 mgKOH/g or less, and even more preferably 0.5 mgKOH/g from the viewpoint of heat storage at a desired set temperature. the following.

In the present invention, other heat storage materials may be mixed together with the above-mentioned (A) component as long as the characteristics of the present invention are not impaired.

Examples of the other thermal storage materials include fatty acid esters, fatty acids, aliphatic hydrocarbons, aliphatic alcohols, and the like other than the aforementioned (A) component.

Examples of fatty acid esters other than the (A) component include fatty acid esters formed from the (a-c) component and alcohols other than the (a-a) component, fatty acid esters formed from the (a-c) component Fatty acid esters formed by carboxylic acids other than the above-mentioned (a-a) component, fatty acid esters formed by carboxylic acids other than the above-mentioned (a-c) component and alcohols other than the (a-a) component, etc.

Examples of carboxylic acids other than the above (a-c) components include monocarboxylic acids having a straight-chain alkyl group with 1 to 7 carbon atoms, and straight-chain alkyl groups with 21 to 30 carbon atoms. Monocarboxylic acids with chained alkyl groups, monocarboxylic acids with branched alkyl groups with 3 to 30 carbon atoms, polycarboxylic acids with alkyl groups with 2 to 30 carbon atoms, polycarboxylic acids with carbon atoms An unsaturated carboxylic acid of an alkyl group having 4 to 30 atoms, and the like.

Examples of alcohols other than the above (a-a) component include monohydric alcohols having a straight-chain alkyl group having 1 to 7 carbon atoms, and straight-chain alkyl alcohols having 21 to 30 carbon atoms. Alkyl monohydric alcohols, monohydric alcohols having branched chain alkyl groups having 3 to 30 carbon atoms, polyols having alkyl groups having 2 to 30 carbon atoms, polyhydric alcohols having 4 or more carbon atoms And 30 or less alkyl unsaturated alcohols, etc.

In addition, the content of the component (A) is preferably 50% by mass to 90% by mass, more preferably 60% by mass to 85% by mass, and still more preferably It is 70 mass % or more and 80 mass % or less, Especially preferably, it is 70 mass % or more and 78 mass % or less. If the content ratio of the (A) component is within the above range, even when using a heat storage material composition containing a very large amount of the (A) component, the holding or retention of the (A) component will be low. It is excellent, and it is also excellent in formability and curability when forming a heat storage molded body, and can prevent the leakage of the (A) component (leakage resistance), and the obtained heat storage molded body can have excellent heat storage properties, which is useful. of.

(heat storage material composition)

The present invention relates to a thermal storage material composition characterized by comprising a thermal storage material including the component (A), a polyol (B), and an isocyanate (C). The thermal storage material composition can be formed in a state where a three-dimensional network structure is formed by the reaction of the polyol (B) and the isocyanate (C), and the thermal storage material containing the component (A) enters the network structure Thermal storage molded body, thereby supporting or holding the thermal storage material containing the above-mentioned (A) component, even when exposed to a high-temperature environment, the thermal storage material containing the above-mentioned (A) component is not easy to spread and leak, and the diffusion-resistant , Excellent leakage resistance, and therefore preferred.

(B) Ingredients

Examples of the polyol (B) include polyester polyol, polyether polyol, acrylic polyol, polycarbonate polyol, polyolefin polyol, polycaprolactone polyol, polytetramethylene Diol polyols, polybutadiene polyols, polyoxypropylene polyols, polyoxypropylene ethylene polyols, epoxy polyols, alkyd polyols, fluoropolyols, silicon polyols, cellulose and/or One kind or two or more kinds of derivatives thereof, polysaccharides such as amylose, and the like can be used.

In the present invention, it is particularly preferable that the polyol (B) contains polyester polyol (B-1) and/or polyether polyol (B-2). Such polyol (B) is excellent in curability, and is easy to uniformly hold or hold the heat storage material in a three-dimensional network structure, and is therefore preferable.

(B-1) Ingredients

It is preferable that the said polyol (B) contains polyester polyol (B-1) ((B-1) component). The said (B-1) component is a component which reacts with the isocyanate (C) mentioned later, and forms a three-dimensional network structure. In particular, by containing the above-mentioned component (B-1), the heat storage material containing the above-mentioned (A) component has excellent support or retention, and the diffusion resistance of the heat-storage material containing the above-mentioned (A) component can be improved. Leak resistance.

Examples of the component (B-1) include polycondensates of polyhydric alcohols and polycarboxylic acids; polycondensates of polyhydric alcohols and hydroxycarboxylic acids; ring-opening polymers of cyclic esters (lactones); , polycarboxylic acid, hydroxycarboxylic acid, and a reactant of three or more components of cyclic ester; castor oil or its modified product, etc.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4- Butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,3-tetraethylene glycol Methylene glycol, 1,4-tetramethylene glycol, 1,2-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1, 3-tetramethylene glycol, 1,4-dimethylolhexane, 2-methyl-1,3-trimethylene glycol, 1,5-pentamethylene glycol, trimethylpentamethylene Diol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 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- Propylene glycol, 2-methyl-1,4-butanediol, 1,6-hexamethylene glycol, 3-methyl-1,5-pentamethylene glycol, 2,4-diethyl- 1,5-pentamethylene glycol, 2-ethyl-1,3-hexanediol, 1,2-octanediol, 1,8-octanediol, 2-methyl-1,8-octanediol Diol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,11-undecanediol, 1,2-dodecanediol, 1,12 -Dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,12 -Octadecanediol, 1,20-Eicosanediol, m-xylene glycol, p-xylene glycol, dihydroxyethoxybenzene, bishydroxyethyl terephthalate, glycerin, diglycerin , trimethylolpropane, bis(trimethylol)propane, trimethylolethane, cyclohexanediols (1,4-cyclohexanediol, cyclohexanedimethanol, etc.), bisphenols ( Bisphenol A, etc.), sugar alcohols (xylitol, sorbitol, etc.), pentaerythritol, dipentaerythritol, 2-methylolpropanediol, ethoxylated trimethylolpropane, etc., or their polycondensates, etc., One or more of these can be used.

Examples of the polyvalent carboxylic acid include malonic acid, maleic acid, maleic anhydride, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane di aliphatic dicarboxylic acids such as tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, etc., 1,4-cyclo Alicyclic dicarboxylic acids such as hexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, terephthalic acid, 2,6-naphthalene dicarboxylic acid, p-phenylene Aromatic dicarboxylic acids such as dicarboxylic acid and trimellitic acid,

Palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, coconut oil fatty acid, palm oil fatty acid, soybean oil fatty acid, hydrogenated soybean oil fatty acid, linseed oil fatty acid, safflower fatty acid, tung oil fatty acid, Semolina oil fatty acid, dehydrated castor oil fatty acid, castor oil fatty acid, grape seed oil fatty acid, black cumin oil fatty acid, pumpkin kernel oil fatty acid, borage oil fatty acid, wheat germ oil fatty acid, rice bran oil fatty acid, peanut oil fatty acid, rapeseed oil fatty acid , sunflower oil fatty acid, corn oil fatty acid, cottonseed oil fatty acid, peanut fatty acid, almond oil fatty acid, pistachio oil fatty acid, almond oil fatty acid, olive oil fatty acid, macadamia nut oil fatty acid, avocado oil fatty acid, seabuckthorn oil fatty acid, Dimers to hexamers of unsaturated fatty acids such as sesame oil fatty acid, hemp oil fatty acid, hazelnut oil fatty acid, primrose oil fatty acid, wild rose oil fatty acid, safflower oil fatty acid, walnut oil fatty acid, etc. can be used. or 2 or more.

Examples of the hydroxycarboxylic acid include 2-hydroxybutyric acid, 2-hydroxyvaleric acid, 3-hydroxyvaleric acid, 3-hydroxyhexanoic acid, 2-hydroxyheptanoic acid, 3-hydroxyheptanoic acid, 2-hydroxy Caprylic acid, 3-hydroxycaprylic acid, 4-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 6-hydroxytetradecanoic acid , 2-hydroxypentadecanoic acid, 10-hydroxyhexadecanoic acid, 11-hydroxyheptadecanoic acid, 10-hydroxyoctadecanoic acid, 12-hydroxyoctadecanoic acid, 10-hydroxynonadecanoic acid, 2 -Hydroxyeicosanoic acid, 2-hydroxyeicosanoic acid, ricinoleic acid, reverse ricinoleic acid, brain glycolic acid, leucine, salicylic acid, glyceric acid, 3-hydroxypropionic acid, 5-hydroxy Valeric acid, 6-hydroxycaproic acid, 7-hydroxyheptanoic acid, 8-hydroxyoctanoic acid, 9-hydroxynonanoic acid, 10-hydroxydecanoic acid, 11-hydroxyundecanoic acid, 12-hydroxydodecanoic acid, 15- Hydroxypentadecanoic acid, 16-hydroxyhexadecanoic acid, 19-hydroxynonadecanoic acid, 22-hydroxybehenic acid, mevalonic acid, pantothenic acid, castor oil fatty acid, dehydrated castor oil fatty acid, etc., Or polycondensates of these acids, etc., one or two or more of these can be used.

Among the ring-opening polymers of cyclic esters, examples of cyclic esters include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

The preparation method of the polyester polyol can be carried out by a conventional method, and a known curing agent, curing catalyst, etc. can also be used as required. In the present invention, as a component constituting the polyester polyol, it is particularly preferable to include polyhydric alcohols, polycarboxylic acids, polycarboxylic acids, One or more kinds of hydroxycarboxylic acids.

Furthermore, as the polyhydric alcohol, dihydric or trihydric alcohols are preferably used. Furthermore, as the polyvalent carboxylic acid, it is preferable to use a divalent or trivalent carboxylic acid.

The number average molecular weight (Mn) of the component (B-1) is preferably from 1000 to 4000, more preferably from 1500 to 3500, still more preferably from 1800 to 3500. When the number average molecular weight of the component (B-1) is within the above range, the curability is excellent and the heat storage material containing the component (A) is easily supported or held uniformly in a three-dimensional network structure, so preferred.

The number of functional groups of the component (B-1) is preferably 2 or more and less than 3, more preferably 2 or more and 2.5 or less. When the number of functional groups of the component (B-1) is within the above range, the curability is excellent and the thermal storage material containing the component (A) is easily supported or held in a three-dimensional network structure, so it is preferable . In addition, the number of functional groups of the component (B-1) is an average value of the number of hydroxyl groups per molecule.

(B-2) Ingredients

The polyol (B) preferably contains a polyether polyol (B-2) (component (B-2)). The said (B-2) component is a component which reacts with the isocyanate (C) mentioned later, and forms a three-dimensional network structure. In particular, the component (B-2) forms a three-dimensional network structure with excellent curability and a stronger three-dimensional network structure, and is easy to uniformly support or maintain the heat storage material containing the component (A) in the three-dimensional network structure. Inside, even if the heat storage material containing the said (A) component has a high content, it can support or hold|maintain.

As the component (B-2), in addition to polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol monoalkyl ether, and polypropylene glycol monoalkyl ether, for example, Examples include copolymers containing multiple alkylene oxides as monomer components (alkylene oxide-another alkylene oxide) such as ethylene oxide-propylene oxide copolymers, and alkylene oxides added with bisphenol A as an initiator. (For example, ethylene oxide, propylene oxide, etc. at least one or more. The following are the same.) The obtained bisphenol A polyether polyol, aromatic amine (such as toluene diamine, diethyltoluene diamine, 4 , 4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalene diamine, triethanolamine, Mannich condensate, etc.) are aromatic amines obtained by adding alkylene oxide to the initiator Polyether polyols, polyether polyols obtained by adding alkylene oxide with glycerin as an initiator, low molecular weight amines (such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, neopentyldiamine, etc.) ) is an amino group-containing polyether polyol obtained by adding an alkylene oxide to an initiator.

The number average molecular weight (Mn) of the component (B-2) is preferably 1,000 to 12,000, more preferably 1,000 to 10,000, further preferably 2,000 to 8,000, particularly preferably 3,000 to 7,000. When the number average molecular weight of the said (B-2) component exists in the said range, since curability will become more excellent, it is preferable.

The number of functional groups of the component (B-2) is preferably 2 or more and 3 or less, more preferably 2 or more and less than 3, and still more preferably 2 or more and 2.5 or less. When the number of functional groups of the above-mentioned (B-2) component is within the above-mentioned range, curability is more excellent, which is preferable. In addition, the number of functional groups of the component (B-2) is an average value of the number of hydroxyl groups per molecule.

Regarding the content ratio (mass ratio) of the above-mentioned (B-1) component and the above-mentioned (B-2) component, (B-1) component: (B-2) component is preferably 50:50 to 100:0, more preferably It is preferably 50:50 to 99:1, more preferably 55:45 to 95:5, particularly preferably 60:40 to 85:15. When the content ratio of the above-mentioned (B-1) component and the above-mentioned (B-2) component is in the said range, since formability and curability are more excellent, it is preferable.

In this invention, polyhydric alcohols other than the said (B-1) component and the said (B-2) component can be used as long as it is the range which does not impair the characteristic of this invention.

Examples of polyols other than the above-mentioned (B-1) component and the above-mentioned (B-2) component include acrylic polyols, polycarbonate polyols, polyolefin polyols, polycaprolactone polyols, Polytetramethylene glycol polyol, polybutadiene polyol, polyoxypropylene polyol, polyoxypropylene ethylene polyol, epoxy polyol, alkyd polyol, fluorine-containing polyol, silicon-containing polyol, cellulose and / or derivatives thereof, polysaccharides such as amylose, and the like.

As the polyolefin polyol, it is possible to use an olefin as a polymer or copolymer backbone (or main chain) component and have at least 2 hydroxyl groups in the molecule (especially at the terminal) and a number average molecular weight (Mn) of 1500 above polyols. The olefin may be an olefin having a carbon-carbon double bond at the terminal (for example, α-olefins such as ethylene and propylene), or an olefin having a carbon-carbon double bond at a position other than the terminal (for example, isobutylene etc.), and further may be dienes (for example, butadiene, isoprene, etc.).

(C) Ingredients

It is preferable that the thermal storage material composition of this invention contains the said isocyanate (C) ((C)component)). The (C) component forms a three-dimensional network structure together with the above-mentioned (B) component, so it is possible to form a heat storage molded body in a state where the heat storage material containing the (A) component is incorporated into the network structure, thereby Holding or holding the heat storage material containing the above-mentioned (A) component, even when exposed to a high-temperature environment, the heat storage material containing the above-mentioned (A) component is difficult to spread and leak, and has excellent diffusion resistance and leakage resistance, and is useful.

The component (C) is isocyanate and is not limited as long as it has an isocyanate group, but preferably there are two or more isocyanate groups in one molecule, more preferably 2.2 or more. Examples of the isocyanate include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, Isocyanate, 1,6-hexamethylene diisocyanate (HMDI), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate Diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexa Methylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanatocaproic acid methyl ester, lysine diisocyanate, dimer acid diisocyanate Aliphatic diisocyanates such as isocyanate and norbornene diisocyanate;

1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanate Methoxy)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate (IPDI), norbornene diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated diisocyanate Alicyclic diisocyanates such as phenylmethane diisocyanate and hydrogenated xylylene diisocyanate;

m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate (TDI), 1,4-naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 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'- Diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, dianisidine diisocyanate, tetramethylenephthalylene Aromatic diisocyanate such as diisocyanate;

1,3-xylylene diisocyanate (XDI), 1,4-xylylene diisocyanate (XDI), ω,ω'-diisocyanate 1,4-diethylbenzene, 1,3- Bis(1-isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methylethyl)benzene, 1,3-bis(α,α-dimethylisocyanate Aromatic aliphatic diisocyanate such as methyl) benzene; Ester), adductation, carbodiimide reaction, etc., derivatives of these isocyanates, mixtures thereof, and reaction products of these with compounds capable of reacting with isocyanate compounds, etc.

As said (C)component, it is preferable to contain the trimer obtained by trimerizing isocyanate (isocyanurate). By using a trimer, it becomes easy to form a three-dimensional network structure together with the said (B) component, and the effect of this invention can be heightened further.

The heat storage material composition of the present invention contains a heat storage material containing the above-mentioned (A) component, the above-mentioned (B) component, and the above-mentioned (C) component. The components are reacted and solidified to obtain a thermal storage molded body.

For the heat storage material composition of the present invention, it is preferable to mix the heat storage material containing the (A) component and the (B) component first, then mix the (C) component, and perform reaction curing to obtain a heat storage material composition. thermoformed body.

In the thermal storage material composition of the present invention, the mixing ratio of the component (B) and the component (C) is preferably 0.75 or more and 2.2 or less, more preferably 0.9 to 2.1, in terms of the NCO/OH ratio (equivalent ratio). , and more preferably 1.05 or more and 2.0 or less. If the NCO/OH ratio is within the above range, the formability and curability are excellent, a stronger three-dimensional network structure is easily formed, and at the same time, it is easy to uniformly support or hold the heat storage material containing the (A) component. Staying within the three-dimensional network is useful.

The heat storage material composition of the present invention may contain, for example, layered clay minerals, surfactants, heat conducting substances, compatibilizers, reaction accelerators, flame retardants, etc. , pigments, aggregates, viscosity regulators, plasticizers, buffers, dispersants, crosslinking agents, pH regulators, preservatives, antifungal agents, antibacterial agents, anti-algae agents, wetting agents, defoamers, flow Additives such as leveling agent, lubricant, dehydrating agent, ultraviolet absorber, antioxidant, light stabilizer, fiber, fragrance, chemical substance adsorbent, photocatalyst, hygroscopic powder and granular body.

(Heat storage molded body)

The present invention relates to a thermal storage molded body, characterized in that it is formed from the thermal storage material composition. The heat storage molded body can be obtained by curing the heat storage material composition, the heat storage molded body can be laminated with various substrates, and the heat storage material composition can be impregnated or impregnated in porous The substrate can be used as a heat storage member by curing it, and the heat storage member can be laminated with various substrates.

From the viewpoint of heat storage properties, the lower limit of the latent heat of the heat storage molded body is preferably 70 J/g or more, more preferably 100 J/g or more, and the upper limit is preferably 220 J/g or less, more preferably 200 J /g or less.

As the phase transition temperature (melting point or freezing point) of the heat storage molded body, for example, in the case of using it as an interior material or exterior material of a building, it is preferably about 10 to 60°C, more preferably 15 to 50°C. ℃ or so.

Examples of the porous substrate include natural fibers such as kapok, hemp, wool, and silk, nylon, Tetoron, acrylic, polyester, polyurethane, Vinylon, rayon, aramid, Organic fibers such as azole, inorganic fibers such as glass and other woven fabrics or non-woven fabrics, paper substrates such as paper and corrugated paper, fiber substrates such as MDF, insulation fiberboard, and particle board, stone boards, gypsum boards, and ALC boards , calcium silicate board, cement wood wool board, plywood and other porous substrates, bamboo charcoal, charcoal and other wood substrates, polyurethane foam board, styrene foam board and other foam resin substrates, etc.

In addition, examples of the various base materials include polystyrene foam, polyurethane foam, acrylic resin foam, phenolic resin foam, polyethylene resin foam, foam rubber, glass wool, rock wool, foam Thermal insulation substrates such as ceramics, resin substrates such as acrylic resins and vinyl resins, glass substrates, metal substrates such as copper, aluminum, iron, brass, zinc, magnesium, and nickel, inorganic substrates such as concrete, or the porous Substrate etc.

The thermal storage material of the present invention, the thermal storage material composition containing the thermal storage material, and the thermal storage molded article obtained by using the thermal storage material composition are mainly suitable for use as interior wall materials and exterior walls of buildings such as houses. materials, ceiling materials, floor materials, their bonding materials, partition materials and other interior materials or exterior materials. In addition, the heat storage material composition of the present invention can be suitably used, for example, as interior materials for floor heating systems, cooling and heating systems, vehicles, etc., industrial products such as machinery or machines, thermoelectric conversion systems, heat insulating materials, extreme cold or fire regions, and arctic regions. Or space protective materials or protective clothing, heat transfer medium, refrigerators or freezers for transporting or storing food or medicine, vending machines, baths or bathrooms, greenhouses, soil, refrigerators, insulation sheets, anti-condensation Sheets, cooling sheets, electrical products, OA machines, equipment (plants), tanks, clothes, curtains, carpets, bedding, daily groceries, etc.

The heat storage material and heat storage material composition of the present invention can be used by various methods, for example, it can be sealed in a box or a bag, or it can be contained in a base material, or it can be encapsulated. It is useful for immobilization to a binding material or the like.

Example

Examples are shown below to clarify the characteristics of the present invention. In addition, this invention is not limited to these Examples.

(Synthesis Example 1: Synthesis of Saturated Fatty Acid Monoester (A-1) 1)

299.1 g of decanoic acid (manufactured by NOF CORPORATION, NAA-102), 400.9 g of hexadecanoic acid, and 400.9 g of hexadecanoic acid were charged into a 1 L four-neck flask equipped with a thermometer, a nitrogen gas inlet tube, a stirrer, a serpentine condenser tube, and an oil-water separator tube with a capacity of 20 mL. Alkanol (manufactured by NOFCORATION, NAA-44).

Take out the reaction water accumulated in the oil-water separation tube, and at the same time, heat the reaction solution to 240°C to measure the acid value of the reaction solution every 1 hour, and carry out the reaction until the decrease of the acid value per 1 hour is below 0.5mgKOH/g.

Then, the reaction solution was depressurized at 220° C. to 30 Torr to remove alcohol and volatile reaction by-products.

After cooling the reaction liquid to 85° C., 1.5 equivalent parts of the sodium hydroxide amount calculated from the acid value was diluted with ion-exchanged water to prepare a 10% by mass aqueous solution, which was added to the reaction liquid and stirred for 1 hour. After stopping stirring, it was left still for 30 minutes, and the water layer separated as the lower layer was removed.

Next, the operation of adding 20% by mass of ion-exchanged water to the reaction liquid, stirring at 85° C. for 10 minutes, standing still for 15 minutes, and removing the separated water layer was repeated five times. Then, it stirred at 100 degreeC and 30 torr for 1 hour, and dehydrated.

Finally, 2% by mass of attapulgite was added to the reaction liquid, stirred at 80° C. and 30 Torr for 1 hour, and filtered to remove the adsorbent. Thus, saturated fatty acid monoester (A-1) 1 was obtained as cetyl caprate.

Capric acid and cetyl alcohol in Synthesis Example 1 were appropriately changed to other compounds shown in Table 1 and Table 2, and the operation was carried out according to Synthesis Example 1, thereby synthesizing the "saturated compound" shown in Table 1 and Table 2. Fatty acid monoester (A-1)", "saturated fatty acid monoester (A-2) and the like".

(acid value and hydroxyl value)

According to JIS K 0070, the acid value (mgKOH/g) and the hydroxyl value (mgKOH/g) of each fatty acid ester shown in Table 1 and Table 2 were measured.

(Measurement test of melting point and freezing point)

Prepare two wooden boards (130mm x 85mm x 6mm) obtained by immersing 22g of each fatty acid ester shown in Table 1 and Table 2 (kept at 50°C), and sandwich a thermocouple between the two wooden boards. , to obtain the test body.

After the obtained test body was left to stand in a thermostat at 39°C for 6 hours, the test body was moved to a thermostat at 19°C and left to stand for 3 hours using a thermocouple, and then left to stand in a thermostat at 39°C for 3 hours. The measurement results (Example 1 shown below) of the temperature change in hours are shown in FIG. 1 . Using the tangent method shown in Fig. 1, the melting point (°C) and freezing point (°C) were measured, and the difference (°C) between the melting point and the freezing point was calculated. Evaluation was performed as described below. Table 3 shows the evaluation results. The temperature in the thermostat is based on the measured phase transition temperature of the fatty acid ester +10°C and -10°C. In addition, when the evaluation was 4, 3, or 2, it was judged to be effective.

In addition, in the same manner as in Example 1, test bodies were produced and evaluated for other Examples, comparative examples, and reference examples (not shown except for Example 1).

4: The difference between melting point and freezing point is less than 1°C.

3: The difference between the melting point and the freezing point is 1°C or more and less than 2°C.

2: The difference between the melting point and the freezing point is 2°C or more and less than 2.5°C.

1: The difference between the melting point and the freezing point is 2.5°C or more.

(Heat storage test 1)

Using each fatty acid ester shown in Table 1 and Table 2, weigh 50 g on a metal container (160 mm x 109 mm x 27 mm), and measure the latent heat with a differential scanning calorimeter (DSC7000X manufactured by Hitachi High-Tech Science Corporation.) (J/g). Specifically, the temperature was changed from 60°C to -40°C at a heating rate of 10°C/min and at a cooling rate of 10°C/min, and then from -40°C to 60°C, and the average of the latent heat of solidification and the latent heat of fusion at this time The value was regarded as the latent heat (J/g), and the heat storage property was evaluated. Evaluation was performed as described below. The evaluation results are shown in Table 3 below. In addition, when the evaluation was 3 or 2, it was judged to be effective.

3: The latent heat is 150 J/g or more.

2: The latent heat is 120 J/g or more and less than 150 J/g.

1: The latent heat is less than 120 J/g.

(diffusion resistance test 1)

Using each fatty acid ester shown in Table 1 and Table 2, 30 g was weighed on a metal container (160 mm x 109 mm x 27 mm), and the mass change before and after storage at 80° C. for 30 days was measured for evaluation. Evaluation was performed as described below. Table 3 shows the evaluation results. In addition, when the evaluation was 4 or 3, it was judged to be effective.

4: The change in mass is less than 1%.

3: The mass change is 1% or more and less than 5%.

2: The mass change is 5% or more and less than 10%.

1: The change in mass is 10% or more.

(hydrolysis resistance test)

Using each fatty acid ester shown in Table 1 and Table 2, the hydrolysis resistance test (94 degreeC x 2 days) based on ASTM-D261 was performed, and the acid value change before and after the test was measured and evaluated. Evaluation was performed as described below. Table 3 shows the evaluation results. In addition, when the evaluation was 3 or 2, it was judged to be effective.

3: The acid value change is less than 0.20.

2: The acid value change is 0.20 or more and less than 0.50.

1: The acid value change is 0.50 or more.

(curability test)

Using the raw materials (compositions) shown in Table 4, mix the raw materials at a temperature of 50°C with the blending amounts shown in Table 5 and Table 6, weigh 50g on a metal container (160mm×109mm×27mm), and heat at 80°C Aging was carried out for 5 hours to obtain a test body. The state of the obtained test body was observed and evaluated. Evaluation was performed as described below. The evaluation results are shown in Table 5 and Table 6. In addition, when the evaluation was 4 or 3, it was judged to be effective.

4: Uniform curing

3: almost uniform curing

2: Uniform curing was not performed, and layer separation was observed.

1: Not cured, always liquid.

(Leak resistance test)

The test body obtained in the above curability test was aged in an atmosphere of 15°C for 12 hours, and then aged at 50°C for 5 hours to obtain a test body. The obtained test body was tilted at 45°, and the amount of heat storage material leaked (missed) from the surface of the test body was measured and evaluated. Evaluation was performed as described below. The evaluation results are shown in Table 5 and Table 6. In addition, when the evaluation was 5, 4, or 3, it was judged to be effective.

5: Leakage of the heat storage material was not observed.

4: Leakage of heat storage material is less than 1%.

3: The leakage amount of the heat storage material is 1% or more and less than 2%.

2: The leakage amount of the heat storage material is 2% or more and less than 3%.

1: The leakage amount of the heat storage material is 3% or more.

(diffusion resistance test 2)

The mass change before and after storing the test body obtained in the said curability test at 80 degreeC for 30 days was measured and evaluated. Evaluation was performed as described below. The evaluation results are shown in Table 5 and Table 6. In addition, when the evaluation was 4 or 3, it was judged to be effective.

4: The change in mass is less than 1%.

3: The mass change is 1% or more and less than 5%.

2: The mass change is 5% or more and less than 10%.

1: The change in mass is 10% or more.

(Heat storage test 2)

Regarding the latent heat (J/g) of the test body obtained in the above-mentioned curability test, the latent heat was measured and evaluated with a differential scanning calorimeter (DSC7000X manufactured by Hitachi High-Tech Science Corporation.). Specifically, the heat storage property was evaluated using the average value of the latent heat of solidification and the latent heat of fusion measured at a heating rate of 10°C/min and a cooling rate of 10°C/min as the latent heat (J/g). Evaluation was performed as described below. The evaluation results are shown in Table 5 and Table 6. In addition, when the evaluation was 3 or 2, it was judged to be effective.

3: The latent heat is 100 J/g or more.

2: The latent heat is 70 J/g or more and less than 100 J/g.

1: The latent heat is less than 70 J/g.

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

In addition, "-" in the above-mentioned Table 6 indicates that the test cannot be carried out because the test body is not cured in the leak resistance test, and it means that the test body is not cured or the leak resistance test is not performed in the diffusion resistance test and heat storage test. Failure to perform the test properly due to large leaks during the test.

From the evaluation results in Table 3 above, it was confirmed that all the characteristics were satisfied by using the component (A-1) as the heat storage material in all the examples.

On the other hand, in Reference Example 1, Comparative Example 1, and Comparative Example 2, the difference between the melting point and the freezing point was larger than that of the examples, and especially in Comparative Example 1 and Comparative Example 2, the desired (A) component was not used, so the melting point The difference from the freezing point was particularly large, and the diffusion resistance and hydrolysis resistance were also inferior to those of Examples.

In addition, from the evaluation results in Table 5 and Table 6, it was confirmed that, in all the examples, the thermal storage molded body obtained using the desired components (A) to (C) had Contributes to curability, heat storage, diffusion resistance and leakage resistance.

On the other hand, in Comparative Examples and Reference Examples, it was not possible to obtain a thermal storage molded article satisfying all of curability, thermal storage properties, diffusion resistance, and leakage resistance at the same time.

Description of drawings

Fig. 1 is the melting point and freezing point measurement test result of the saturated fatty acid monoester used in embodiment 1.

Claims (12)

1. A heat storage material comprising a saturated fatty acid monoester (A) obtained by reacting a saturated aliphatic monocarboxylic acid having a linear alkyl group having 8 to 20 carbon atoms and a saturated aliphatic monohydric alcohol having a linear alkyl group having 8 to 20 carbon atoms.

2. The heat storage material according to claim 1, wherein the saturated fatty acid monoester (A) contains a saturated fatty acid monoester (A-1) obtained by reacting a saturated aliphatic monocarboxylic acid (a-c) having a linear alkyl group having 8 to 20 carbon atoms (Nc) with a saturated aliphatic monohydric alcohol (a-a) having a linear alkyl group having 8 to 20 carbon atoms (Na) and satisfying the following formula (1),

(1) (Nc)＜(Na)。

3. the heat storage material according to claim 2, wherein the saturated fatty acid monoester (A-1) satisfies the following formula (2),

(2) 22≤(Nc+Na)≤32。

4. the heat-accumulative material of claim 2 or 3, wherein the saturated fatty acid monoester (A-1) satisfies the following formula (3),

(3) 4≤(Na-Nc)≤8。

5. a heat-accumulative material composition comprising the heat-accumulative material of any one of claims 1-4, polyol (B) and isocyanate (C).

6. The heat storage material composition according to claim 5, wherein the polyol (B) contains a polyester polyol (B-1) and/or a polyether polyol (B-2).

7. The heat storage material composition according to claim 5 or 6, wherein the content ratio of the heat storage material in the total amount of the heat storage material composition is 50 mass% or more and 95 mass% or less.

8. The heat storage material composition according to claim 6 or 7, wherein the (B-1) component contains a polyester polyol having a number average molecular weight of 1000 or more and 4000 or less and a functional group number of 2 or more and less than 3.

9. The heat storage material composition according to any one of claims 6 to 8, wherein the (B-2) component contains a polyether polyol having a number average molecular weight of 1000 to 12000, and a functional group number of 2 to 3.

10. The heat storage material composition according to any one of claims 5 to 9, wherein the component (C) contains a trimer of isocyanate.

11. The heat storage material composition according to any one of claims 6 to 10, wherein a mixing ratio of a total amount of the (B-1) component and the (B-2) component to the (C) component is 0.75 to 2.2 in terms of NCO/OH ratio.

12. A thermal storage molded body formed from the thermal storage material composition according to any one of claims 5 to 11.