JP6967943B2 - Heat storage material composition - Google Patents

Description

The present invention relates to a heat storage material composition containing a latent heat storage material, a method for producing the same, and a heat storage body including a porous substrate and the heat storage material composition.

In recent homes, as represented by smart houses, we are aiming to build comfortable homes that do not emit carbon dioxide, with the keywords "energy saving," "energy creation," and "energy storage." On the other hand, there is an idea of a passive house, and attention is being paid to housing construction that realizes high energy saving and comfort by providing high-performance heat insulation performance. In any house, it is indispensable to improve the heat insulation performance of the house and the performance against the thermal environment. Against this background, research and development of building materials with heat storage that can store heat on the floors and walls of houses and provide energy-saving and comfortable living spaces are becoming active.

For example, natural energy such as sunlight, heat energy generated by heating and cooling equipment, or heat energy generated in daily life is stored in a latent heat storage material such as normal paraffin, and heat is absorbed and dissipated in response to fluctuations in the outside temperature. Proposals and attempts have been made to minimize the temperature change in the room by doing this.

The present applicant discloses in Patent Document 1 a heat storage body in which a porous substrate is impregnated with a heat storage material composition containing a latent heat storage material. Since the latent heat storage material utilizes the latent heat required for the phase transition between the solid phase and the liquid phase, the outflow of the liquefied latent heat storage material becomes a problem. It is disclosed that a porous substrate is impregnated with a heat storage material composition containing a predetermined amount of a hydrogenated styrene-based thermoplastic elastomer.

On the other hand, Patent Document 2 states that even under a heat cycle in which solidification and melting phase transitions are repeated, there is no exudation or phase separation from the material supporting the latent heat storage material n-paraffin, and the material supporting the latent heat storage material at a high concentration. As a latent heat storage material composition capable of maintaining a stable gel-like body even when mixed with, a latent heat storage material (A) made of n-paraffin having 12 or more and 50 or less carbon atoms that can store heat by latent heat is 30% by mass or more 93. Saturation of the styrene-ethylene / propylene block copolymer, which is 5% by mass or less and is the supporting material (B) that supports the latent heat storage material (A), is 6% by mass or more and 70% by mass or less, and has 12 or more and 24 or less carbon atoms. Alternatively, it is characterized by containing at least one gelling agent (C) selected from unsaturated carboxylic acid, hydroxycarboxylic acid, or a metal salt thereof in a proportion of 0.5% by mass or more and 5% by mass or less. The latent heat storage material composition is disclosed.

WO2015 / 174523 Japanese Unexamined Patent Publication No. 2017-31327

The impregnation of the heat storage material composition, which is described in Patent Document 1 in which a predetermined amount of a hydrogenated styrene-based thermoplastic elastomer is blended with the latent heat storage material, impregnates the porous substrate with the heat storage material composition at a temperature of about 80 ° C to 100 ° C. This is done by immersing the porous substrate in the melt. Since the latent heat storage material described in Patent Document 1 has a large temperature dependence of the viscosity of the melt in the temperature range of 80 ° C to 100 ° C, the present inventors have impregnated the porous substrate with the melt. I found a new problem that it is difficult to stabilize.

The present inventors also ensure that the heat storage material composition in which the styrene-ethylene / propylene block copolymer described in Patent Document 2 is combined with the latent heat storage material ensures the impregnation property into the panel substrate during heat melting. When the viscosity of the mixture of latent heat storage material and elastomer is adjusted, the latent heat storage material can be easily separated under the heat cycle (cold heat treatment) of heating and cooling in the range of 5 to 60 ° C. I found a problem.

The present inventors have a heat storage material having a sufficiently small melt viscosity in a temperature range of 80 ° C. or higher, a small temperature dependence of the melt viscosity, and high stability against cold heat treatment in a temperature range of 60 ° C. or lower. As a result of diligent studies for the purpose of providing the composition, the following inventions have been completed.

First of all, the present invention
It contains a latent heat storage material, a hydrogenated styrene-based thermoplastic elastomer, and an oil gelling agent.
The elastomer comprises a block copolymer of triblock or higher, comprising at least a soft segment and hard segments bonded to both ends of the soft segment.
The oil gelling agent is a saturated or unsaturated carboxylic acid having 12 or more and 24 or less carbon atoms, a metal salt of a saturated or unsaturated carboxylic acid having 12 or more and 24 carbon atoms or less, and a hydroxycarboxylic acid having 12 or more and 24 carbon atoms or less. It contains one or more selected from the group consisting of an acid, a metal salt of a hydroxycarboxylic acid having 12 or more and 24 or less carbon atoms, dibenzylidene sorbitol, and an amino acid-based oil gelling agent.
The melt viscosity at 80 ° C. is 200 mPa · s or less,
An X mass portion of the elastomer is contained with respect to 100 parts by mass of the latent heat storage material, and the X mass portion is the mixture of 100 parts by mass of the latent heat storage material and the X mass portion of the elastomer at 60 ° C. The amount is such that the melt viscosity is 3500 mPa · s or more.
The present invention relates to a heat storage material composition.

The heat storage material composition of the present invention has a sufficiently small melt viscosity when heated at 80 ° C. or higher, and its temperature dependence is small. Therefore, when the melt of the heat storage material composition is impregnated into the porous substrate. The impregnation amount is stable and there is little variation. Further, the heat storage material composition of the present invention has a high melt viscosity at 60 ° C. of 3500 mPa · s or more and contains a thermoplastic elastomer of triblock or more, so that it can be used for cold heat treatment in a temperature range of 60 ° C. or lower. High stability.

In a preferred embodiment, the heat storage material composition of the present invention has a melt viscosity at 100 ° C. of 150 mPa · s or less.

The heat storage material composition of the present invention of this aspect is preferable because it is easy to impregnate the porous substrate to a saturated state.

In another preferred embodiment of the heat storage material composition of the present invention, the latent heat storage material is paraffin having a phase change temperature in the range of 15 ° C. or higher and 35 ° C. or lower.

The heat storage material composition of the present invention in this aspect is suitable for residential use because the phase change temperature corresponds to the temperature of the living environment.

In another preferred embodiment of the heat storage composition of the present invention, the elastomer comprises a styrene-ethylene / butylene-styrene block copolymer (SEBS).

The heat storage material composition of the present invention of this aspect is preferable because it has particularly high resistance to cold heat treatment in a temperature range of 60 ° C. or lower.

In another preferred embodiment of the heat storage composition of the present invention, the oil gelling agent comprises 12-hydroxystearic acid or a metal salt thereof.

12-Hydroxystearic acid or a metal salt thereof has a melting point of 75 ° C. Therefore, the heat storage material composition of the present invention of this aspect tends to be solidified at 60 ° C. and can be stably held on the porous substrate.

Secondly, the present invention
The above-mentioned method for producing a heat storage material composition of the present invention.
A melt-kneading step in which a latent heat storage material, a hydrogenated styrene-based thermoplastic elastomer, and an oil gelling agent are melt-kneaded.
The present invention relates to a method including a cooling step of cooling the mixture produced in the melt-kneading step.
According to the method of the present invention, a heat storage material composition having the above-mentioned advantageous properties can be produced.

The present invention is third,
Porous substrate and
The present invention relates to a heat storage body including at least the heat storage material composition impregnated in the porous substrate.
The heat storage body of the present invention has little exudation from the porous substrate of the heat storage material composition in the temperature range of 60 ° C. or lower.

The heat storage material composition of the present invention has a sufficiently small melt viscosity when heated at 80 ° C. or higher, and its temperature dependence is small. Therefore, when the melt of the heat storage material composition is impregnated into the porous substrate. The impregnation amount is stable and there is little variation. Further, the mixture of the latent heat storage material and the elastomer constituting the heat storage material composition of the present invention has a high melt viscosity at 60 ° C. of 3500 mPa · s or more and contains a thermoplastic elastomer of triblock or more. High stability against cold heat treatment in the temperature range below ° C.

The heat storage material in which the heat storage material composition of the present invention is impregnated in the porous base material is preferable because the heat storage material composition does not exude from the porous base material in a temperature range of 60 ° C. or lower.

<1. Material>
1.1. Latent heat storage material The latent heat storage material that can be used in the present invention is, for example, a latent heat storage material that undergoes a phase change from a solid phase to a liquid phase due to indoor heating, heat from sunlight, etc., and the phase change temperature (melting point) is preferable. Is in the range of 5 ° C to 60 ° C, more preferably 15 ° C or higher, more preferably 18 ° C or higher, more preferably 35 ° C or lower, more preferably 28 ° C or lower, and even more preferably. It is in the range of 15 ° C to 35 ° C, more preferably in the range of 18 ° C to 28 ° C. In the present specification, the phase change temperature and the melting point refer to the values at 1 atm. The phase change temperature is also called the phase transition temperature.

For example, in the summer, for the purpose of storing the cold temperature of air cooled by air conditioning, shaded air, or nighttime air and absorbing the heat when the room temperature is high, it is higher than the cold temperature and higher than the high room temperature to be lowered. It is preferable to use a latent heat storage material having a low phase change temperature. Examples of such a phase change temperature include 22 to 28 ° C. Also, in winter, for the purpose of storing the warm temperature of the air warmed by heating, the sun's air, or the daytime air and dissipating it when the temperature drops, it is lower than the warm temperature and lower than the low room temperature that should be raised. It is preferable to use a latent heat storage material having a high phase change temperature. Examples of such a phase change temperature include 18 to 26 ° C.

The latent heat storage material is composed of at least one selected from the group consisting of n-hexadecane, n-heptadecane, n-octadecan, and n-nonadecan (may be a mixture of two or more) or the like. Saturated aliphatic hydrocarbons such as n-paraffin and paraffin wax (preferably linear saturated aliphatic hydrocarbons) containing at least one of the above and typically having carbon atoms in the range of 16 to 24 carbon atoms; It is composed of at least one selected from the group consisting of 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene and the like (may be a mixture of two or more) or the above. Monovalent or polyvalent non-valent, such as α-olefins (preferably linear α-olefins), including at least one, typically having a carbon number in the range of 16 to 26 (preferably 24 or less). Saturated aliphatic hydrocarbons (preferably linear monovalent or polyunsaturated aliphatic hydrocarbons); at least one selected from the group consisting of octanoic acid, capric acid, lauric acid, and myristic acid (two). A medium chain composed of (may be a mixture of the above) or the like, or containing at least one of the above, typically having a carbon number in the range of 6 to 24 carbon atoms, preferably 8 to 14 carbon atoms. Or long-chain fatty acids; esters of the above fatty acids; polyether compounds such as polyethylene glycol (for example, molecular weight 500 to 1000); inorganic salts such as sodium sulfate hydrate, calcium chloride hydrate, sodium sulfate decahydrate and the like. be able to. Preferably, the latent heat storage material is selected from the group consisting of the saturated aliphatic hydrocarbon, the monovalent or polyunsaturated aliphatic hydrocarbon, the medium-chain or long-chain fatty acid, the ester of the fatty acid, and the polyether compound. One or more mixtures, more preferably one or more mixtures selected from the group consisting of the saturated aliphatic hydrocarbons and the monovalent or polyunsaturated aliphatic hydrocarbons. It is more preferably one or a mixture of two or more selected from the group consisting of the saturated aliphatic hydrocarbon and the α-olefin. For example, n-octadecane can be selected if it melts at 28 ° C., and n-hexadecane can be selected if it melts at 18 ° C. Further, a plurality of latent heat storage materials having different phase change temperatures may be mixed and used. When the α-olefin is used as the latent heat storage material, a mixture of a plurality of the α-olefins having different carbon atoms can be used.

1.2. Hydrogenated Styrene-based Thermoplastic Elastomer The hydrogenated styrene-based thermoplastic elastomer used in the present invention includes a block copolymer of triblock or higher containing at least a soft segment and a hard segment bonded to both ends of the soft segment. It is characterized by. Since the soft segment has a high affinity with the latent heat storage material, in the heat storage material composition containing the hydrogenated styrene-based thermoplastic elastomer having the above structure and the latent heat storage material, the soft segment of the elastomer is integrated with the latent heat storage material due to its affinity. To become. On the other hand, the hard segments at both ends of the soft segment form pseudo-crosslinks with the hard segments of other molecules when the temperature drops, forming a three-dimensional network structure. Therefore, unlike the case of using a diblock-structured hydrogenated styrene-based thermoplastic elastomer such as styrene-ethylene / propylene block copolymer (SEP), the above-mentioned triblock-structured hydrogenated styrene-based thermoplastic elastomer and latent heat are used. In the heat storage material composition containing the heat storage material, the viscosity of the melt increases remarkably as the temperature decreases. Therefore, the heat storage material composition of the present invention has a feature that the separation of the latent heat storage material is suppressed in the cold heat treatment in which heating and cooling are repeated in the range of 5 to 60 ° C. The styrene-ethylene / propylene block copolymer described in Patent Document 2 is a copolymer having a diblock structure in which one hard segment and one soft segment are adjacent to each other. It has been confirmed in Experiment 3 that the polymer does not have the above-mentioned effect.

Examples of the hydrogenated styrene-based thermoplastic elastomer include styrene-ethylene / butylene-styrene block copolymer (SEBS), styrene-ethylene / propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene / propylene. Examples thereof include those containing at least one polymer (which may be a mixture of two or more) selected from the group consisting of -styrene block copolymers (SEEPS). As the copolymer, at least one selected from the group consisting of SEBS and SEEPS is preferable. SEBS is a polystyrene-poly (ethylene / butylene) -polystyrene block copolymer, SEPS is a polystyrene-poly (ethylene / propylene) -polystyrene block copolymer, and SEEPS is a polystyrene-poly (ethylene-ethylene / propylene) -polystyrene. It can also be referred to as a block copolymer. The range of the styrene content in the hydrogenated styrene-based thermoplastic elastomer is not particularly limited, but the styrene content is preferably in the range of 25 to 35% by mass with respect to the entire molecule.

The weight average molecular weight of the copolymer constituting the hydrogenated styrene-based thermoplastic elastomer is preferably 60,000 or more, more preferably 75,000 or more, still more preferably 85,000 or more, and most preferably 90,000 or more. be. The weight average molecular weight of the hydrogenated styrene-based thermoplastic elastomer is preferably 250,000 or less, more preferably 200,000 or less, and most preferably 150,000 or less. When the weight average molecular weight of the copolymer is in this range, the outflow of the heat storage material composition from the porous substrate can be suppressed, and the viscosity of the heat storage material composition at the time of melting is sufficiently low to impregnate the porous substrate. The effect of facilitating is particularly high.

In the present invention, the weight average molecular weight is determined as a standard polystyrene equivalent value based on the measurement by gel permeation chromatography (GPC). Tetrahydrofuran can be used as the eluent for GPC measurement. As the column for GPC, a column in which TSKgel GMHXL, TSKgel G4000HXL, and TSKgel G5000HXL manufactured by Tosoh Corporation are connected in series can be used. As the GPC measuring device, a gel permeation chromatograph (HLC-8020) manufactured by Tosoh Corporation can be used.

1.3. Oil Gelling Agent The oil gelling agent used in the present invention is a saturated or unsaturated carboxylic acid having 12 or more and 24 or less carbon atoms, a metal salt of a saturated or unsaturated carboxylic acid having 12 or more and 24 or less carbon atoms, and a carbon number of carbon atoms. It contains one or more selected from the group consisting of a hydroxycarboxylic acid of 12 or more and 24 or less, a metal salt of a hydroxycarboxylic acid having 12 or more and 24 or less carbon atoms, dibenzylidene sorbitol, and an amino acid-based oil gelling agent, preferably one or more. Is a saturated or unsaturated carboxylic acid having 12 or more and 24 or less carbon atoms, a metal salt of a saturated or unsaturated carboxylic acid having 12 or more and 24 carbon atoms or less, a hydroxycarboxylic acid having 12 or more and 24 carbon atoms or less, and carbon. Includes one or more selected from the group consisting of metal salts of hydroxycarboxylic acids having a number of 12 or more and 24 or less.

The heat storage material composition containing only the elastomer and the latent heat storage material has a problem that the melt viscosity when heated at 80 ° C. is high and the temperature dependence of the melt viscosity in the temperature range of 80 ° C. or higher is large. rice field. The present inventors have an unexpected phenomenon that the heat storage material composition further blended with the oil gelling agent has a sufficiently low melt viscosity in a temperature range of 80 ° C. or higher and a small temperature dependence of the melt viscosity. The present invention was completed.
The oil gelling agent has the property of solidifying into a gel when added to warm cooking oil and cooled.

As a saturated or unsaturated carboxylic acid having 12 or more and 24 or less carbon atoms, or a hydroxycarboxylic acid having 12 or more and 24 or less carbon atoms, if the number of carbon atoms is 12 or more and 24 or less, it is saturated, unsaturated or linear. , It may be branched. For example, lauric acid, myristic acid, pentadecylic acid, palmitic acid, palmitoleic acid, margaric acid, stearic acid, oleic acid, vaccenic acid, rinoleic acid, arachidic acid, arachidic acid, behenic acid, lignoceric acid, 12-hydroxystearic acid, Examples thereof include ricinoleic acid. Examples of these metal salts include salts of lithium, potassium, sodium, magnesium, calcium, barium, aluminum and the like.

The dibenzylideneacetone sorbitol is preferably a 1: 2 dehydration condensate of D-sorbitol and benzaldehyde.

As the amino acid-based oil gelling agent, derivatives such as amides, esters, and amine salts of N-acylamino acids are preferable. Specific examples of the amino acid-based oil gelling agent include N-lauroyl glutamic acid di-n-butyramide.

The melting point of the oil gelling agent is preferably a temperature equal to or higher than the phase change temperature of the latent heat storage material, preferably a temperature 10 ° C. or higher, more preferably 20 ° C. or higher higher than the phase change temperature of the latent heat storage material.
As the oil gelling agent, 12-hydroxystearic acid or a metal salt thereof is particularly preferable.

1.4. Porous base material The porous base material that can be used in the present invention is a base material having fine voids that can be impregnated and held with the heat storage material composition. Specifically, it may be a porous base material containing a material having fine voids capable of impregnating and holding a latent heat storage material, and the material is not limited.

Specific examples of the material of the porous base material include wood-based boards such as particle boards and wood fiber boards (MDF, insulation boards, hard boards, etc.). In addition to this, inorganic boards such as gypsum boards and calcium silicate boards; mineral boards in which mineral substances are molded into a board shape; boards in which inorganic fibers such as glass wool, carbon fiber, and metal fibers are integrated can be mentioned. can.

The overall shape of the porous substrate is not particularly limited, and may be various shapes such as a plate shape, a columnar shape, and a block shape. Further, the porous substrate having various shapes may be bent. Here, the bending process may be performed before the step of impregnating the heat storage material composition, or may be performed after the step. When the porous substrate is plate-shaped, its thickness is not particularly limited, but is usually 3 to 30 mm, preferably 5 to 20 mm. It is preferable that the entire porous substrate is impregnated with the heat storage material composition, but the present invention is not limited to this, and only a part of the surface layer portion of the porous substrate may be impregnated with the heat storage material composition. ..

The smaller the density of the porous substrate, the easier it is for the porous substrate to be impregnated with the heat storage material composition. As the porous substrate, the density of the portion impregnated with the heat storage material composition (density before impregnation treatment) is preferably 0.1 g / cm ³ or more, more preferably 0.2 g / cm ³ or more. It is preferably less than 0.9 g / cm ^3. The density of the porous substrate is generally preferably low in order to increase the impregnation rate, for example, ^{less than 0.8 g / cm 3} , 0.7 g / cm ³ or less, 0.6 g / cm ^3. The density is preferably 0.5 g / cm ^{3 or less.}

<2. Heat storage material composition>
2.1. Melt Viscosity The heat storage material composition of the present invention is characterized by having a melt viscosity at 80 ° C. of 200 mPa · s or less.

When the porous base material is impregnated with the heat storage material composition, it is usually melted in a temperature range of 80 ° C. or higher and the porous base material is immersed in the molten liquid. When the melt viscosity of the heat storage material composition is in this range, it is preferable because it is easily impregnated into the porous substrate. Further, the heat storage material composition containing a latent heat storage material, a hydrogenated styrene-based thermoplastic elastomer, and an oil gelling agent and having a melt viscosity at 80 ° C. of 200 mPa · s or less has a temperature of 80 ° C. or higher. Since the temperature dependence of the viscosity is small in the region, even if the temperature at the time of immersion of the porous substrate fluctuates slightly, the amount of impregnation into the porous substrate does not vary, which is preferable.

The melt viscosity of the heat storage material composition of the present invention at 80 ° C. is more preferably 170 mPa · s or less.

Further, the heat storage material composition of the present invention preferably has a melt viscosity at 100 ° C. of 150 mPa · s or less, and particularly preferably 30 mPa · s or less. Such a heat storage material composition can be rapidly impregnated into the porous substrate when melted at around 100 ° C.

The viscosity can be measured by a method using a Brookfield type rotational viscometer (B type viscometer) specified in JIS Z8803-2011 and JIS K7117-1. As the B-type viscometer, ABS-100 manufactured by Toki Sangyo is used, and measurement can be performed under the conditions of rotor size: No. 1, No. 2, and rotation speed: 6 to 60 rpm.

2.2. Amount of Thermoplastic Elastomer The heat storage material composition of the present invention contains X mass parts of the elastomer with respect to 100 parts by mass of the latent heat storage material, where X mass parts means 100 parts by mass of the latent heat storage material and X mass. A further feature is that the melt viscosity of the mixture composed of the above-mentioned elastomer in the portion at 60 ° C. is 3500 mPa · s or more. The heat storage material composition of the present invention containing X parts by mass of the elastomer with respect to 100 parts by mass of the latent heat storage material and further containing an oil gelling agent has high stability against cold heat treatment in a temperature range of 60 ° C. or lower. Therefore, it is preferable.

The specific example of the X part by mass is not particularly limited, but is typically 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 17.5 parts by mass or less, still more preferably 12.5 parts by mass. It is 5 parts or less, typically 6 parts by mass or more, and more preferably 7.5 parts by mass or more. When the amount of the hydrogenated styrene-based thermoplastic elastomer added is within the above range, the outflow of the heat storage material composition from the porous substrate can be suppressed, and the viscosity of the heat storage material composition at the time of melting is sufficiently low to the porous substrate. The effect of facilitating impregnation is particularly high.

<3. Method for manufacturing heat storage material composition>
The heat storage material composition of the present invention is
A melt-kneading step in which a latent heat storage material, a hydrogenated styrene-based thermoplastic elastomer, and an oil gelling agent are melt-kneaded.
It can be produced by a method including a cooling step of cooling the mixture produced in the melt-kneading step.

The melt-kneading step includes melt-kneading the latent heat storage material, the hydrogenated styrene-based thermoplastic elastomer, and the oil gelling agent in the range of, for example, 80 ° C. to 140 ° C., preferably 100 ° C. to 120 ° C.

The cooling step includes cooling the mixture produced in the melt-kneading step in the range of, for example, 60 ° C to 0 ° C, preferably 40 ° C to 10 ° C.

<4. Heat storage body>
The heat storage body of the present invention is
Porous substrate and
It includes at least the heat storage material composition impregnated in the porous substrate.

As a method of impregnating the porous substrate with the heat storage material composition, the heat storage material composition is heated and melted in a temperature range of 80 ° C. or higher, preferably 80 to 110 ° C., and melted. Further, a method of immersing the porous substrate for an appropriate time, for example, 1 to 10 minutes can be exemplified.

The impregnation rate of the heat storage material composition in the porous substrate is preferably 180% or more, more preferably 200% or more, and more preferably 210% or more. The upper limit of the impregnation rate is not particularly limited, but is usually 250% or less.

The impregnation rate (%) can be expressed by the following equation.
Impregnation rate = (Weight of heat storage body after impregnation-Weight of porous substrate before impregnation) / (Weight of porous substrate before impregnation) x 100 (%)
That is, the impregnation rate is the ratio of the weight of the heat storage material composition impregnated in the porous substrate (= weight of the heat storage body after impregnation-weight of the porous substrate before impregnation) to the weight of the porous substrate before impregnation. Is expressed with the latter as 100%.

In the following tests, "parts" means "parts by mass".
In the following tests, the viscosity was measured by the method using a Brookfield type rotational viscometer (B type viscometer) specified in JIS Z8803-2011 and JIS K7117-1. As the B-type viscometer, ABS-100 manufactured by Toki Sangyo was used, and the measurement was performed under the conditions of rotor size: NO1 and rotation speed: 6 to 60 rpm.

In the following tests, the weight average molecular weight of the thermoplastic elastomer was determined as a standard polystyrene equivalent value based on the measurement by gel permeation chromatography (GPC) under the following conditions.

Measuring equipment: Gel Permeation Chromatograph manufactured by Tosoh Corporation (HLC-8020)
Column: Column in which TSKgel GMHXL, TSKgel G4000HXL, and TSKgel G5000HXL manufactured by Tosoh Corporation are connected in series Eluent: Tetrahydrofuran

<1. Experiment 1>
In this experiment, a composition obtained by adding one or more of a styrene-based thermoplastic elastomer (SEBS) and an oil gelling agent (12-hydroxystearic acid) to a latent heat storage material (normal paraffin) at 70 to 100 ° C. The heat melt viscosity, the physical properties at 60 ° C., and the presence or absence of separation of the latent heat storage material in the cold heat test (5 ° C./60 ° C.) were investigated.

1.1. Sample A normal paraffin (16 carbon atoms) having a melting point of 18 ° C. was used as the latent heat storage material.
A styrene-ethylene / butylene-styrene block copolymer (referred to as "SEBS (1)") having a weight average molecular weight of 110,000 or a weight average molecular weight of 80,000 as a hydrogenated styrene-based thermoplastic elastomer having a triblock structure. Styrene-ethylene / butylene-styrene block copolymer (referred to as "SEBS (2)") was used.
12-Hydroxystearic acid was used as the oil gelling agent.

1.2. Test method To 100 parts of normal paraffin having a melting point of 18 ° C., one or more of SEBS (1), SEBS (2) and 12-hydroxystearic acid was added so as to have a mass portion shown in Table 1 and 100 parts were added. The compositions of Samples 1 to 7 were prepared by heating at ~ 130 ° C. and melting and mixing.

Each of the prepared samples was melted at 100 ° C., 90 ° C., 80 ° C. or 70 ° C., and the viscosity was measured using the above viscometer.

100 g of the composition was placed in a 200 mL container and heated at 60 ° C. for 24 hours, and it was observed whether the composition had fluidity or solidified.

Furthermore, the cold test was carried out by the following procedure. In the same manner as above, 100 g of the heat storage material composition was placed in a container and solidified at room temperature, and then cooling at 5 ° C. for 24 hours and heating at 60 ° C. for 24 hours were repeated 5 times with the container rolled over. Then, it was evaluated whether or not the latent heat storage material was separated from the sample.

1.3. Results The results are shown in Table 1.
Sample 1, which contains 15 parts of SEBS (1) in 100 parts of the latent heat storage material but does not contain the oil gelling agent, has a high heat-melt viscosity at 70 ° C. or higher, and has a high temperature dependence of viscosity. rice field. In addition, it was difficult to maintain the gelled state (solidified state) at 60 ° C.

Samples 2 to 6 containing SEBS (1) and / or SEBS (2) and 12-hydroxystearic acid in the amounts shown in Table 1 in 100 parts of the latent heat storage material have a low heat-melt viscosity at 70 ° C. or higher. The temperature dependence of the viscosity was low, and the gelled state (solidified state) was maintained at 60 ° C. However, separation (exudation) of the latent heat storage material was observed in the cold heat test.

On the other hand, Sample 7 (Example) containing 10 parts of SEBS (1) and 5 parts of 12-hydroxystearic acid in 100 parts of the latent heat storage material has a low heat-melt viscosity at 70 ° C. or higher. The temperature dependence of the viscosity was low, the gelled state (solidified state) was maintained at 60 ° C., and the latent heat storage material was not separated (exuded) in the thermal test.

<2. Experiment 2>
In this experiment, samples A-1, B-1, C-1, D-1, E-1, F- in which one or more styrene-based thermoplastic elastomers (SEBS) were added to a latent heat storage material (normal paraffin). The heat melt viscosity of No. 1 at 60 to 100 ° C. was examined. In this experiment, 70 of Samples A-2, B-2, C-2, D-2, E-2, and F-2 in which an oil gelling agent (12-hydroxystearic acid) was further added to the sample. The hot melt viscosity at ~ 100 ° C. and the presence / absence of separation of the latent heat storage material in the cold test (5 ° C./60 ° C.) were examined.

2.1. Sample A normal paraffin having a melting point of 18 ° C. (16 carbon atoms) or a normal paraffin having a melting point of 28 ° C. (18 carbon atoms) was used as the latent heat storage material.
SEBS (1) or SEBS (2) was used as the hydrogenated styrene-based thermoplastic elastomer having a triblock structure, as in Experiment 1.
12-Hydroxystearic acid was used as the oil gelling agent.

2.2. Test method The mass of one or more of SEBS (1), SEBS (2) and 12-hydroxystearic acid with respect to 100 parts of normal paraffin having a melting point of 18 ° C. or 100 parts of normal paraffin having a melting point of 28 ° C. is shown in Table 2. Samples A-1, B-1, C-1, D-1, E-1, F-1, A-2, The compositions of B-2, C-2, D-2, E-2 and F-2 were prepared. Samples A-2, B-2, C-2, D-2, E-2, and F-2 are samples A-1, B-1, C-1, D-1, E-1, F, respectively. -1 is further blended with 5 parts of 12-hydroxystearic acid.

The viscosity of each of the prepared samples was measured using the above viscometer in a state of being melted at 100 ° C., 90 ° C., 80 ° C., 70 ° C. or 60 ° C. However, for the samples A-2, B-2, C-2, D-2, E-2, and F-2, the melt viscosity at 60 ° C. was not measured.

For samples A-2, B-2, C-2, D-2, E-2, and F-2, a thermal test was performed in the same procedure as in Experiment 1, and whether or not the latent heat storage material was separated. Was evaluated.

2.3. Results The results are shown in Table 2.
Samples A-2, B-2, C-2, D-2, E-2, in which SEBS (1) and / or SEBS (2) and 12-hydroxystearic acid are mixed with a latent heat storage material (normal paraffin). It was found that F-2 had a low heat melt viscosity at 70 ° C. or higher (for example, a melt viscosity at 80 ° C. was 200 mPa · s or less), and the temperature dependence of the viscosity was low. It can be seen that these samples are easily impregnated into the porous substrate.

Furthermore, in the samples C-2, E-2, and F-2, separation of the latent heat storage material was not observed in the cold heat test. On the other hand, in the samples A-2, B-2 and D-2, the separation of the latent heat storage material was confirmed in the cold heat test.

Samples C-2, E-2, and F-2 are prepared by blending 5 parts of 12-hydroxystearic acid with Samples C-1, E-1, and F-1, respectively, and Samples A-2 and B- 2 and D-2 are samples A-1, B-1, and D-1 mixed with 5 parts of 12-hydroxystearic acid, respectively. The melt viscosities of the samples C-1, E-1, and F-1 at 60 ° C. are 3500 mPa · s or more, whereas the melt viscosities of the samples A-1, B-1, and D-1 at 60 ° C. are high. It was less than 3500 mPa · s.

Therefore, the type and blending amount of SEBS were adjusted so that the melt viscosity of the latent heat storage material (normal paraffin) to which only the hydrogenated styrene-based thermoplastic elastomer (SEBS) was added at 60 ° C. was 3500 mPa · s or more. Further, by blending an oil gelling agent (12-hydroxystearic acid), it is supported that a composition without separation of the latent heat storage material can be obtained.

<3. Experiment 3>
In this experiment, a composition (Samples G-1, H-1, I-1) in which a styrene-ethylene / propylene block copolymer (SEP) was added as a hydrogenated styrene-based thermoplastic elastomer to a latent heat storage material (normal paraffin). ) Was examined by heating and melting at 60 to 100 ° C. In this experiment, the heat melt viscosity of the samples G-2, H-2, and I-2 to which the oil gelling agent (12-hydroxystearic acid) was further added to the sample at 70 to 100 ° C. and the thermal test The presence or absence of separation of the latent heat storage material at (5 ° C / 60 ° C) was investigated.

3.1. Sample A normal paraffin (16 carbon atoms) having a melting point of 18 ° C. was used as the latent heat storage material.
As a diblock-structured hydrogenated styrene-based thermoplastic elastomer, a styrene-ethylene / propylene block copolymer having a weight average molecular weight of 220,000 (referred to as "SEP (1)") or styrene having a weight average molecular weight of 300,000. -An ethylene / propylene block copolymer (referred to as "SEP (2)") was used.
12-Hydroxystearic acid was used as the oil gelling agent.

3.2. Test method To 100 parts of normal paraffin having a melting point of 18 ° C., one or more of SEP (1), SEP (2) and 12-hydroxystearic acid was added so as to have a mass portion shown in Table 3 and 100 parts were added. The compositions of Samples G-1, H-1, I-1, G-2, H-2, and I-2 were prepared by heating at ~ 130 ° C. and melting and mixing. Samples G-2, H-2, and I-2 are prepared by further blending 5 parts of 12-hydroxystearic acid with Samples G-1, H-1, and I-1, respectively.

The viscosity of each of the prepared samples was measured using the above viscometer in a state of being melted at 100 ° C., 90 ° C., 80 ° C., 70 ° C. or 60 ° C. However, for the samples G-2, H-2, and I-2, the melt viscosity at 60 ° C. was not measured.

Further, the samples G-2, H-2, and I-2 were subjected to a cold heat test in the same procedure as in Experiment 1 to evaluate whether or not the latent heat storage material was separated.

3.3. Results The results are shown in Table 3.
Samples G-1, H-1, and I-1 in which SEP (1) or SEP (2) is mixed with a latent heat storage material (normal paraffin) have a temperature dependence of the melt viscosity in the temperature range of 70 to 100 ° C. It was found to be low. Further, in the samples G-2 and H-2 in which 12-hydroxystearic acid was further added to the samples G-1 and H-1, separation of the latent heat storage material was observed in the cold heat test. That is, even if 12-hydroxystearic acid is further added to the sample in which SEP (1) or SEP (2) is added to the latent heat storage material (normal paraffin), the viscosity at the time of impregnation into the porous substrate is reduced. It was confirmed that it is difficult to achieve both stable retention of the latent heat storage material (resistant to the cold test).

From the above results, when a hydrogenated styrene-based thermoplastic elastomer having a diblock structure is used for solidifying the latent heat storage material, even if an oil gelling agent is further added, the amount is low when impregnated into the porous substrate. It can be seen that it is difficult to achieve both viscosity increase and stable retention of the latent heat storage material (cold heat test resistance).

<4. Experiment 4>
In this experiment, sample 10 in which a styrene-based thermoplastic elastomer (SEBS) was mixed with a latent heat storage material (normal paraffin), and a styrene-based thermoplastic elastomer (SEBS or SEP) and oil gelled in a latent heat storage material (normal paraffin). The heat melt viscosity of Samples 8, 9 and 11 containing the agent (12-hydroxystearic acid) at 100 ° C. or 80 ° C. was examined. In this experiment, the impregnation rate of the porous substrate into the porous substrate was measured when the porous substrate was immersed in the samples 8 to 11 melted at 100 ° C. for 1 to 10 minutes.

4.1. Sample A normal paraffin having a melting point of 18 ° C. (16 carbon atoms) or a normal paraffin having a melting point of 28 ° C. (18 carbon atoms) was used as the latent heat storage material.
SEBS (1) described in Experiment 1 was used as a hydrogenated styrene-based thermoplastic elastomer having a triblock structure. The SEP (2) described in Experiment 3 was used as the hydrogenated styrene-based thermoplastic elastomer having a diblock structure.
12-Hydroxystearic acid was used as the oil gelling agent.
A wood fiber board (insulation board, dimensions: 200 × 200 × thickness 5 mm) was used as the porous base material.

4.2. Test method For 100 parts of normal paraffin with a melting point of 18 ° C or 100 parts of normal paraffin with a melting point of 28 ° C, one or more of SEBS (1), SEP (2) and 12-hydroxystearic acid is added to the mass shown in Table 4. The composition was prepared as a sample 8 to 11 by adding the mixture in portions, heating at 100 to 130 ° C. and melting and mixing.

The viscosity of each of the prepared samples was measured using the above-mentioned viscometer in a state of being melted at 100 ° C. or 80 ° C.

The porous substrate was immersed in each sample heated and melted at 100 ° C. for 1 minute, 3 minutes, 5 minutes or 10 minutes, and then withdrawn. The weight of the porous substrate was determined before and after impregnation, and the impregnation rate was calculated by the following formula.
Impregnation rate = (Weight of heat storage body after impregnation-Weight of porous substrate before impregnation) / (Weight of porous substrate before impregnation) x 100 (%)

4.3. Results The results are shown in Table 4.
A blend of 10 parts of SEBS (1) and 5 parts of 12-hydroxystearic acid in 100 parts of latent heat storage material (normal paraffin), the melt viscosity at 80 ° C is 200 mPa · s or less, and the melt viscosity at 100 ° C. When the porous substrate was immersed in the melt of Samples 8 and 9 at 100 ° C., which had a viscosity of 30 mPa · s or less, the impregnation rate reached a saturated state (about 220%) after immersion for 3 minutes. The impregnation rate was sufficiently high even after soaking for 1 minute.

On the other hand, when the porous substrate is immersed in a melt of sample 10 containing only 15 parts of SEBS (1) in 100 parts of latent heat storage material (normal paraffin) at 100 ° C., it is impregnated by immersion for 5 minutes or more. The rate reached a saturated state (about 220%), but when the impregnation time was short, the impregnation rate was greatly reduced.

When the porous substrate is immersed in the melt of sample 11 at 100 ° C., which is a mixture of 100 parts of latent heat storage material (normal paraffin), 5 parts of SEP (2) and 5 parts of 12-hydroxystearic acid. The impregnation rate did not reach the saturated state (about 220%) even when immersed for 10 minutes.

Claims (7)

It contains a latent heat storage material, a hydrogenated styrene-based thermoplastic elastomer, and an oil gelling agent.
The elastomer comprises a block copolymer of triblock or higher, comprising at least a soft segment and hard segments bonded to both ends of the soft segment.
The oil gelling agent is a saturated or unsaturated carboxylic acid having 12 or more and 24 or less carbon atoms, a metal salt of a saturated or unsaturated carboxylic acid having 12 or more and 24 carbon atoms or less, and a hydroxycarboxylic acid having 12 or more and 24 carbon atoms or less. It contains one or more selected from the group consisting of an acid, a metal salt of a hydroxycarboxylic acid having 12 or more and 24 or less carbon atoms, dibenzylidene sorbitol, and an amino acid-based oil gelling agent.
The melt viscosity at 80 ° C. is 200 mPa · s or less,
An X mass portion of the elastomer is contained with respect to 100 parts by mass of the latent heat storage material, and the X mass portion is the mixture of 100 parts by mass of the latent heat storage material and the X mass portion of the elastomer at 60 ° C. The amount is such that the melt viscosity is 3500 mPa · s or more.
A heat storage material composition characterized by this. The heat storage material composition according to claim 1, wherein the melt viscosity at 100 ° C. is 150 mPa · s or less. The heat storage material composition according to claim 1 or 2, wherein the latent heat storage material is paraffin having a phase change temperature in the range of 15 ° C. or higher and 35 ° C. or lower. The heat storage material composition according to any one of claims 1 to 3, wherein the elastomer contains a styrene-ethylene / butylene-styrene block copolymer (SEBS). The heat storage material composition according to any one of claims 1 to 4, wherein the oil gelling agent contains 12-hydroxystearic acid or a metal salt thereof. The method for producing a heat storage material composition according to any one of claims 1 to 5.
A melt-kneading step in which a latent heat storage material, a hydrogenated styrene-based thermoplastic elastomer, and an oil gelling agent are melt-kneaded.
A method comprising a cooling step of cooling the mixture produced in the melt-kneading step. Porous substrate and
A heat storage body comprising at least the heat storage material composition according to any one of claims 1 to 5, which is impregnated with the porous substrate.