WO2021187220A1 - 蓄熱材組成物 - Google Patents
蓄熱材組成物 Download PDFInfo
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- WO2021187220A1 WO2021187220A1 PCT/JP2021/009160 JP2021009160W WO2021187220A1 WO 2021187220 A1 WO2021187220 A1 WO 2021187220A1 JP 2021009160 W JP2021009160 W JP 2021009160W WO 2021187220 A1 WO2021187220 A1 WO 2021187220A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
Definitions
- the present invention relates to a heat storage material composition.
- a latent heat storage material composition utilizing latent heat generated or absorbed at the time of a phase change from a liquid to a solid or a phase change from a solid to a liquid is known.
- the latent heat storage material composition is used, for example, in a heat storage system for heating and cooling a building.
- the latent heat storage material composition is simply referred to as a "heat storage material composition”.
- the heat storage material composition has a stable and sufficient heat storage effect in a required temperature range. Therefore, for example, when the heat storage material composition is used in the heat storage system for heating and cooling of the building, the heat storage material composition has a large amount of heat storage, and the melting point and freezing point of the heat storage material composition are in the heating and cooling of the building. It is desirable to meet or approximate the conditions of use.
- the melting point means the temperature at which the heat storage material composition melts in the heating process for heating
- the freezing point means the temperature at which the heat storage material composition solidifies in the cooling process for cooling.
- the melting point of the heat storage material composition used in the heat storage system for heating and cooling of buildings is 27 ° C. or lower.
- the heat storage material composition used in the heat storage system for heating and cooling of a building has a small melting temperature range and a large latent heat of melting in this melting temperature range.
- the heat storage material composition used in the heat storage system for heating and cooling of a building has a large latent heat of melting in a small melting temperature range.
- Patent Document 1 discloses a heat storage material composition in which ammonium salts such as ammonium chloride, ammonium bromide, and ammonium nitrate are added to calcium chloride hexahydrate.
- the heat storage material composition of Patent Document 1 is not suitable for use as a heat storage system for heating and cooling of buildings because the melting point exceeds 27 ° C. Further, the heat storage material composition of Patent Document 1 has a large melting temperature range.
- An object of the present invention is to provide a heat storage material composition having a melting point of 27 ° C. or lower and a large latent heat of melting in a small melting temperature range.
- the heat storage material composition according to the aspect of the present invention contains a main agent mixture composed of calcium chloride hexahydrate, ammonium chloride, and water, and the calcium chloride hexahydrate in 100% by mass of the main agent mixture.
- a main agent mixture composed of calcium chloride hexahydrate, ammonium chloride, and water
- the calcium chloride hexahydrate in 100% by mass of the main agent mixture.
- Sample No. It is a specific parameter expression figure which showed the composition of a heat storage material composition by a specific parameter.
- Sample No. It is a graph which shows the supercooling degree of B1 to B13.
- Sample No. It is a graph which shows the supercooling degree of C1 to C23.
- the heat storage material composition according to the present embodiment contains a main agent mixture consisting of calcium chloride hexahydrate, ammonium chloride, and water.
- the base mixture consists of calcium chloride hexahydrate, ammonium chloride and water.
- Calcium chloride hexahydrate is a heat storage substance. Calcium chloride hexahydrate generally causes a large supercooling phenomenon.
- Ammonium chloride is a melting point depressant.
- the calcium chloride hexahydrate (CaCl 2 ⁇ 6H 2 O) , may be a known.
- 100% by mass of the main agent mixture contains calcium chloride hexahydrate, usually 45.0 to 55.0% by mass, preferably 50.0 to 54.0% by mass. It preferably contains 51.0 to 53.0% by mass.
- 100% by mass of the main agent mixture means that the total amount of calcium chloride hexahydrate, ammonium chloride, and water is 100% by mass.
- the latent heat of melting at a melting point of 27 ° C. or lower and 25 ° C. or higher and 28 ° C. or lower tends to increase.
- ammonium chloride As ammonium chloride (NH 4 Cl), known ones can be used.
- 100% by mass of the main agent mixture contains ammonium chloride, usually 1.0 to 5.0% by mass, preferably 2.0 to 4.0% by mass, and more preferably 2. Contains 5 to 3.5% by mass.
- the content of ammonium chloride is within the above range, the latent heat of melting at a melting point of 27 ° C. or lower and 25 ° C. or higher and 28 ° C. or lower tends to increase.
- Water for example, pure water can be used.
- 100% by mass of the base mixture is water, usually 43.0 to 50.0% by mass, preferably 45.5 to 48.5% by mass, more preferably 46.0. Includes up to 48.0% by mass.
- the latent heat of melting at a melting point of 27 ° C. or lower and 25 ° C. or higher and 28 ° C. or lower tends to increase.
- the melting point of the heat storage material composition is 27 ° C. or lower and the latent heat of melting at 25 ° C. or higher and 28 ° C. or lower. Is preferable because it tends to be large.
- FIG. 1 is a specific parameter representation diagram showing the composition of the heat storage material composition with specific parameters.
- a pentagonal region satisfying the above equations (1) to (5) is indicated by reference numeral R.
- the sides satisfying each of the above equations (1) to (5) are designated as F1 to F5, respectively.
- the heat storage material composition according to the present embodiment further contains a supercooling inhibitor because supercooling is further suppressed.
- the degree of supercooling is indicated by, for example, the degree of supercooling.
- the supercooling degree means the difference between the freezing point T F and supercooling temperature T S (T F ⁇ T S ).
- Supercooling temperature T S can be measured by a surface temperature change of the sample was placed RTD in a thermostatic chamber.
- overcooling inhibitor examples include strontium chloride hexahydrate, strontium hydroxide octahydrate, barium hydroxide octahydrate, strontium chloride, strontium hydroxide, barium hydroxide, calcium hydroxide, and aluminum hydroxide.
- At least one hypercooling inhibitor selected from the group is used.
- the supercooling inhibitor is preferably strontium hydroxide octahydrate or strontium hydroxide because supercooling is further suppressed.
- the heat storage material composition according to the present embodiment contains 100 parts by mass of the main agent mixture and 0.3 to 1.1 parts by mass of strontium hydroxide octahydrate or strontium hydroxide, supercooling is further suppressed. Therefore, it is preferable.
- the heat storage material composition according to the present embodiment has a degree of supercooling of 1 to 2 when it contains 100 parts by mass of the main agent mixture and 0.5 to 1.0 parts by mass of strontium hydroxide octahydrate or strontium hydroxide. It is more preferable because it tends to be in the range of .5 ° C.
- the heat storage material composition according to the present embodiment further contains a supercooling suppressing additive in addition to the supercooling suppressing agent because supercooling is further suppressed.
- overcooling inhibitor examples include decanoic acid, diatomaceous earth, rayon, octadecane, monododecyl sodium phosphate, 1-propanol, polyester non-woven fabric, polyester fiber, alumina, bromooctadecane, 2-propanol, and glycerin.
- the supercooling inhibitor is composed of the above substances, the degree of supercooling tends to be in the range of 0.9 to 3.9 ° C, which is preferable.
- polyester non-woven fabric for example, Della (registered trademark) ⁇ is used.
- polyester fiber for example, a fiber obtained by crushing Della is used.
- the supercooling inhibitor is strontium hydroxide octahydrate
- the supercooling inhibitor is decanoic acid, diatomaceous earth, rayon, octadecane, monododecyl sodium phosphate, 1-propanol, polyester non-woven fabric, polyester fiber,
- one or more substances selected from the group consisting of alumina are preferable because supercooling is further suppressed.
- the heat storage material composition according to the present embodiment includes 100 parts by mass of the main agent mixture, 0.3 to 1.1 parts by mass of strontium hydroxide octahydrate, and 0.4 to 1.1 parts by mass of the supercooling inhibitor. When and is included, the degree of supercooling tends to be in the range of 0.9 to 3.9 ° C, which is preferable.
- the heat storage material composition according to the present embodiment includes 100 parts by mass of the main agent mixture, 0.5 to 1.0 parts by mass of strontium hydroxide octahydrate, and 0.4 to 1.1 parts by mass of the supercooling inhibitor. When and is included, the degree of supercooling tends to be in the range of 0.9 to 3.9 ° C, which is more preferable.
- the heat storage material composition according to the present embodiment includes 100 parts by mass of the main agent mixture, 0.5 to 1.0 parts by mass of strontium hydroxide octahydrate, and 0.5 to 1.0 parts by mass of the supercooling inhibitor. Including and, the degree of supercooling is more likely to be in the range of 0.9 to 3.9 ° C, which is more preferable.
- the supercooling inhibitor is strontium hydroxide
- the supercooling inhibitor is from octadecane, rayon, bromooctadecan, 1-propanol, alumina, polyester non-woven fabric, 2-propanol, glycerin, and monododecyl sodium phosphate. It is preferable that one or more substances selected from the above group are used because supercooling is further suppressed.
- the heat storage material composition according to the present embodiment contains 100 parts by mass of the main agent mixture, 0.3 to 1.1 parts by mass of strontium hydroxide, and 0.05 to 3.1 parts by mass of the supercooling inhibitor. This is preferable because the degree of supercooling tends to be in the range of 0.9 to 3.9 ° C.
- the heat storage material composition according to the present embodiment contains 100 parts by mass of the main agent mixture, 0.3 to 1.1 parts by mass of strontium hydroxide, and 0.4 to 3.1 parts by mass of the supercooling inhibitor. This is more preferable because the degree of supercooling tends to be in the range of 0.9 to 3.9 ° C.
- the heat storage material composition according to the present embodiment contains 100 parts by mass of the main agent mixture, 0.5 to 1.0 part by mass of strontium hydroxide, and 0.5 to 3.0 parts by mass of the supercooling inhibitor. This is even more preferable because the degree of supercooling is more likely to be in the range of 0.9 to 3.9 ° C.
- the heat storage material composition according to the present embodiment further contains a thickener because phase separation is suppressed and the stability of the heat storage performance over a long period of time is improved.
- thickeners include sodium silicate, water glass, polyacrylic acid, sodium polyacrylate, polycarboxylate polyether polymer, sodium acrylate / maleic acid copolymer, and acrylate / sulfonic acid type.
- One type of thickener is used.
- the heat storage material composition according to the present embodiment further contains a melting point lowering agent
- the melting point of the heat storage material composition can be further lowered. Therefore, it is preferable that the heat storage material composition further contains a melting point depressant because it is easy to adjust the melting point of the heat storage material composition to match or approach the optimum melting point of the heat storage system.
- a melting point lowering agent at least one selected from the group consisting of, for example, sodium chloride, potassium chloride, sodium nitrate, sodium bromide, ammonium chloride, ammonium bromide, ammonium sulfate, ammonium nitrate, ammonium phosphate, and urea. Seed melting point lowering agents are used.
- the heat storage material composition according to the present embodiment has a melting point of 27 ° C. or lower and a latent heat of melting at 25 ° C. or higher and 28 ° C. or lower of 165 J / g or higher.
- the melting point was measured by a differential scanning calorimetry (DSC). Specifically, for the heat absorption peak at the time of melting measured by DSC, the intersection of the baseline on the melting start side and the tangent line at the inflection point on the melting start side of the peak is obtained, and the temperature of this intersection is set to the melting point. And said.
- DSC differential scanning calorimetry
- the latent heat of melting at 25 ° C. or higher and 28 ° C. or lower was measured by DSC.
- the latent heat of melting calculated by integrating the endothermic peak at the time of melting measured by DSC in the range of 25 ° C. to 28 ° C. was defined as the latent heat of melting at 25 ° C. or higher and 28 ° C. or lower.
- Example 1 (Preparation of heat storage material composition) Calcium chloride hexahydrate (CaCl 2 ⁇ 6H 2 O, manufactured by Kishida Chemical Co., Ltd., special grade) and ammonium chloride (NH 4 Cl, Kishida Chemical Co., Ltd., special grade) and a pure water, a total of about 5g A predetermined amount was mixed so as to be. The amounts of calcium chloride hexahydrate, ammonium chloride and pure water were blended in such an amount that the composition of the obtained heat storage material composition became the composition shown in Table 1. When the obtained mixture was boiled in hot water at 50 ° C. or higher, a heat storage material composition was obtained (Sample No. A13). The heat storage material composition consists of calcium chloride hexahydrate, ammonium chloride, and pure water, and consists only of a so-called base mixture.
- the content of calcium chloride hexahydrate in 100% by mass of the main agent mixture is CA% by mass
- the content of ammonium chloride is NH% by mass
- the content of water is W% by mass.
- FIG. 1 is a specific parameter representation diagram showing the composition of the heat storage material composition with specific parameters.
- a pentagonal region satisfying the above equations (1) to (5) is indicated by reference numeral R.
- the sides satisfying each of the above equations (1) to (5) are designated as F1 to F5, respectively.
- Sample No. The composition of the heat storage material composition of A13 is plotted in FIG.
- the plot existing in the pentagonal region R satisfying the above equations (1) to (5) is indicated by a symbol ⁇ , and exists outside the region R not satisfying the above equations (1) to (5).
- the plot is indicated by the symbol x.
- Sample No. The plot of the heat storage material composition of A13 is indicated by the symbol ⁇ .
- the latent heat of melting calculated by integrating the heat absorption peak at the time of melting obtained by DSC in the range of 25 ° C. to 28 ° C. was defined as the latent heat of melting at 25 ° C. or higher and 28 ° C. or lower.
- Example 1 [Examples 2 to 10, Comparative Examples 1 to 19] The amount of each component added was adjusted so that the obtained heat storage material composition had the composition shown in Table 1, and the heat storage material composition was prepared in the same procedure as in Example 1 (Sample Nos. A1 to A12, A14-A29). (Specific parameter representation diagram) Sample No. For A1 to A12 and A14 to A29, the composition of the heat storage material composition was plotted in FIG. 1 in the same manner as in Example 1.
- the melting point of the heat storage material composition is 27 ° C. or less and 25. It can be seen that the latent heat of melting at ° C. or higher and 28 ° C. or lower is large.
- Example 11 to 23 (Preparation of heat storage material composition)
- the main agent mixture of Example 2 (Sample No. A14) was prepared. It was also prepared supercooling inhibitor as strontium hydroxide octahydrate Sr (OH) 2 ⁇ 8H 2 O ( produced by Fuji Film Wako Pure Chemical Industries, Ltd.).
- supercooling inhibitor as strontium hydroxide octahydrate Sr (OH) 2 ⁇ 8H 2 O ( produced by Fuji Film Wako Pure Chemical Industries, Ltd.).
- the sample No. A14 100 parts by mass of the base resin mixture, Sr (OH) and 2 ⁇ 8H 2 O, by mixing the supercooling control additive, a necessary to prepare a heat storage material composition (Sample No.B1 ⁇ B13) ..
- the supercooling inhibitory additives shown in Table 2 are as follows. ⁇ Decanoic acid: manufactured by Kishida Chemical Co., Ltd. ⁇ Diatomaceous earth: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., average particle size 50 ⁇ m -Rayon: Made by Unitika Ltd., fiber diameter 1 mm, fiber length 10 mm ⁇ Octadecan: Fuji Film Wako Pure Chemical Industries, Ltd. ⁇ Monododecyl sodium phosphate: Tokyo Chemical Industry Co., Ltd. ⁇ 1-Propanol: Kishida Chemical Co., Ltd.
- Dila crushed fiber Fiber made by crushing polyester non-woven fabric Dila (registered trademark) manufactured by Unitika Ltd.
- Alumina Alumina powder manufactured by Kishida Chemical Co., Ltd.
- the supercooling temperature was measured by changing the surface temperature of a sample in which a resistance temperature detector was installed in a constant temperature bath.
- the degree of supercooling was calculated by subtracting the supercooling temperature from the melting point.
- Examples 24-44, Comparative Examples 20 and 21 (Preparation of heat storage material composition) First, the main agent mixture of Example 2 (Sample No. A14) was prepared. Further, strontium hydroxide Sr (OH) 2 (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was prepared as a supercooling inhibitor. Next, in the blending amount shown in Table 3, the sample No. A heat storage material composition was prepared by mixing 100 parts by mass of the main agent mixture of A14, Sr (OH) 2, and if necessary, a supercooling inhibitory additive (Sample Nos. C1 to C23).
- the supercooling inhibitory additives shown in Table 3 are as follows. ⁇ Octadecane: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. ⁇ Rayon: manufactured by Unitika Ltd., fiber diameter 1 mm, fiber length 10 mm -Diatomaceous earth: manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., average particle size 50 ⁇ m ⁇ Bromooctadecane: manufactured by Kishida Chemical Co., Ltd. ⁇ 1-propanol: manufactured by Kishida Chemical Co., Ltd. ⁇ Alumina: manufactured by Kishida Chemical Co., Ltd.
- the present invention it is possible to provide a heat storage material composition having a melting point of 27 ° C. or lower and a large latent heat of melting in a small melting temperature range.
- the latent heat of melting in the small melting temperature range was defined as the latent heat of melting at 25 ° C. or higher and 28 ° C. or lower.
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Abstract
Description
X=CA/(CA+W) (P1)
[数2]
Y=NH/(CA+NH+W) (P2)
[数3]
X-51.75>0 (1)
[数4]
52.75-X>0 (2)
[数5]
4.25-Y>0 (3)
[数6]
1.2245X+Y-66.367>0 (4)
[数7]
-2.1569X+Y+110.27>0 (5)
本実施形態に係る蓄熱材組成物は、塩化カルシウム6水和物と、塩化アンモニウムと、水と、からなる主剤混合物を含む。
主剤混合物は、塩化カルシウム6水和物と、塩化アンモニウムと、水と、からなる。塩化カルシウム6水和物は、蓄熱物質である。塩化カルシウム6水和物は、一般的に、大きな過冷却現象を生じる。塩化アンモニウムは、融点降下剤である。
塩化カルシウム6水和物(CaCl2・6H2O)としては、公知のものを用いることができる。
塩化アンモニウム(NH4Cl)としては、公知のものを用いることができる。
水としては、例えば純水を用いることができる。
蓄熱材組成物の組成は、主剤混合物100質量%中における、塩化カルシウム6水和物、塩化アンモニウム、及び水の含有量を用いて、下記式(P1)及び(P2)で規定されるパラメーターX及びYで表すことができる。具体的には、主剤混合物100質量%中における、塩化カルシウム6水和物の含有量をCA質量%、塩化アンモニウムの含有量をNH質量%、水の含有量をW質量%としたときに、下記式(P1)及び(P2)で規定されるパラメーターX及びYで表すことができる。
[数8]
X=CA/(CA+W) (P1)
[数9]
Y=NH/(CA+NH+W) (P2)
[数10]
X-51.75>0 (1)
[数11]
52.75-X>0 (2)
[数12]
4.25-Y>0 (3)
[数13]
1.2245X+Y-66.367>0 (4)
[数14]
-2.1569X+Y+110.27>0 (5)
パラメーターX及びYが、式(1)~(5)を満たす範囲を図1に示す。図1は、蓄熱材組成物の組成を特定のパラメーターで示した特定パラメータ表現図である。図1において、上記式(1)~(5)を満たす五角形の領域を符号Rで示す。また、符号Rの五角形の外周を構成する各辺のうち、上記式(1)~(5)のそれぞれを満たす辺を、それぞれ、F1~F5と示す。
本実施形態に係る蓄熱材組成物は、過冷却抑制剤をさらに含むと、過冷却がより抑制されるため好ましい。過冷却の度合いは、例えば、過冷度で示される。ここで、過冷度とは、凝固点TFと過冷却温度TS(TF≧TS)との差分を意味する。過冷却温度TSは、恒温槽内に測温抵抗体を設置したサンプルの表面温度変化により測定することができる。
本実施形態に係る蓄熱材組成物は、過冷却抑制剤に加えて過冷却抑制添加剤をさらに含むと、過冷却がさらに抑制されるため好ましい。
本実施形態に係る蓄熱材組成物は、増粘剤をさらに含むと、相分離が抑制されることにより、長期にわたる蓄熱性能の安定性が向上するため好ましい。このような増粘剤としては、例えば、ケイ酸ナトリウム、水ガラス、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリカルボキシレートポリエーテルポリマー、アクリル酸・マイレン酸共重合体ナトリウム、アクリル酸・スルホン酸系モノマー共重合体ナトリウム、アクリルアミド・ジメチルアミノエチルメタクリラートジメチル硫酸塩共重合物、アクリルアミド・アクリル酸ソーダ共重合物、ポリエチレングリコール、ポリプロピレングリコール、高吸水樹脂(SAP)、カルボキシメチルセルロース(CMC)、CMCの誘導体、カラギーナン、カラギーナンの誘導体、キサンタンガム、キサンタンガムの誘導体、ペクチン、ペクチンの誘導体、デンプン、デンプンの誘導体、コンニャク、寒天、層状ケイ酸塩、及びこれらの物質の複合物質からなる群より選択される少なくとも1種の増粘剤が用いられる。
本実施形態に係る蓄熱材組成物は、融点降下剤をさらに含むと、蓄熱材組成物の融点をさらに降下させることができる。このため、蓄熱材組成物が融点降下剤をさらに含むと、蓄熱材組成物の融点を、蓄熱システムの最適な融点に一致又は近づける調整が容易になるため好ましい。このような融点降下剤としては、例えば、塩化ナトリウム、塩化カリウム、硝酸ナトリウム、臭化ナトリウム、塩化アンモニウム、臭化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、リン酸アンモニウム、及び尿素からなる群より選択される少なくとも1種の融点降下剤が用いられる。
本実施形態に係る蓄熱材組成物は、融点が27℃以下で、かつ25℃以上28℃以下での融解潜熱が165J/g以上である。
(蓄熱材組成物の作製)
塩化カルシウム6水和物(CaCl2・6H2O、キシダ化学株式会社製、特級)と、塩化アンモニウム(NH4Cl、キシダ化学株式会社製、特級)と、純水とを、合計約5gになるように所定量混合した。塩化カルシウム6水和物、塩化アンモニウム及び純水の量は、得られる蓄熱材組成物の組成が表1に示す組成になるような量で配合した。得られた混合物を50℃以上で湯煎したところ、蓄熱材組成物が得られた(試料No.A13)。
蓄熱材組成物は、塩化カルシウム6水和物、塩化アンモニウム、及び純水からなり、いわゆる主剤混合物のみからなる。
[数15]
X=CA/(CA+W) (P1)
[数16]
Y=NH/(CA+NH+W) (P2)
[数17]
X-51.75>0 (1)
[数18]
52.75-X>0 (2)
[数19]
4.25-Y>0 (3)
[数20]
1.2245X+Y-66.367>0 (4)
[数21]
-2.1569X+Y+110.27>0 (5)
さらに、得られたパラメーターX及びYを図1に示した。図1は、蓄熱材組成物の組成を特定のパラメーターで示した特定パラメータ表現図である。図1において、上記式(1)~(5)を満たす五角形の領域を符号Rで示す。また、符号Rの五角形の外周を構成する各辺のうち、上記式(1)~(5)のそれぞれを満たす辺を、それぞれ、F1~F5と示す。
試料No.A13の蓄熱材組成物の組成を図1にプロットした。なお、図1において、上記式(1)~(5)を満たす五角形の領域R内に存在するプロットを記号○で示し、上記式(1)~(5)を満たさない領域R外に存在するプロットを記号×で示した。試料No.A13の蓄熱材組成物のプロットは記号○で示した。
蓄熱材組成物を20mg採取し、示差走査熱量計(DSC)による熱分析を行った。得られた融解時の吸熱ピークについて、融解開始側のベースラインと、ピークの融解開始側の変曲点での接線と、の交点を求め、この交点の温度を融点とした。
DSCで得られた融解時の吸熱ピークについて、25℃~28℃の範囲内で積分して算出した融解潜熱を、25℃以上28℃以下での融解潜熱とした。
得られる蓄熱材組成物が表1に示す組成になるように、各成分の添加量を調整し、実施例1と同様の手順にて蓄熱材組成物を作製した(試料No.A1~A12、A14~A29)。
(特定パラメータ表現図)
試料No.A1~A12、A14~A29につき、実施例1と同様にして、蓄熱材組成物の組成を図1にプロットした。
(蓄熱材組成物の作製)
はじめに、実施例2の主剤混合物(試料No.A14)を用意した。また、過冷却抑制剤として水酸化ストロンチウム8水和物Sr(OH)2・8H2O(富士フィルム和光純薬株式会社製)を用意した。
次に、表2に示す配合量で、試料No.A14の主剤混合物の100質量部と、Sr(OH)2・8H2Oと、必要により過冷却抑制添加剤と、を混合して、蓄熱材組成物を作製した(試料No.B1~B13)。
・デカン酸:キシダ化学株式会社製
・珪藻土:富士フィルム和光純薬株式会社製、平均粒径50μm
・レーヨン:ユニチカ株式会社製、繊維径1mm、繊維長10mm
・オクタデカン:富士フィルム和光純薬株式会社製
・リン酸モノドデシルナトリウム:東京化成工業株式会社製
・1-プロパノール:キシダ化学株式会社製
・ディラ(不織布):ユニチカ株式会社製、ポリエステル製不織布ディラ(登録商標)
・ディラ解砕繊維:ユニチカ株式会社製、ポリエステル製不織布ディラ(登録商標)を解砕した繊維
・アルミナ:キシダ化学株式会社製アルミナ粉末
また、過冷度を以下のようにして測定した。
恒温槽内に測温抵抗体を設置したサンプルの表面温度変化により、過冷却温度を測定した。融点から過冷却温度を差し引いて過冷度を算出した。
(蓄熱材組成物の作製)
はじめに、実施例2の主剤混合物(試料No.A14)を用意した。また、過冷却抑制剤として水酸化ストロンチウムSr(OH)2(富士フィルム和光純薬株式会社製)を用意した。
次に、表3に示す配合量で、試料No.A14の主剤混合物の100質量部と、Sr(OH)2と、必要により過冷却抑制添加剤と、を混合して、蓄熱材組成物を作製した(試料No.C1~C23)。
・オクタデカン:富士フィルム和光純薬株式会社製
・レーヨン:ユニチカ株式会社製、繊維径1mm、繊維長10mm
・珪藻土:富士フィルム和光純薬株式会社製、平均粒径50μm
・ブロモオクタデカン:キシダ化学株式会社製
・1-プロパノール:キシダ化学株式会社製
・アルミナ:キシダ化学株式会社製アルミナ粉末
・ディラ(不織布):ユニチカ株式会社製、ポリエステル製不織布ディラ(登録商標)
・2-プロパノール:キシダ化学株式会社製
・グリセリン:キシダ化学株式会社製
・リン酸モノドデシルナトリウム:東京化成工業株式会社製
・MgCl2:キシダ化学株式会社製塩化マグネシウム
Claims (13)
- 塩化カルシウム6水和物と、
塩化アンモニウムと、
水と、からなる主剤混合物を含み、
前記主剤混合物100質量%中における、前記塩化カルシウム6水和物の含有量をCA質量%、前記塩化アンモニウムの含有量をNH質量%、前記水の含有量をW質量%としたときに下記式(P1)及び(P2)で規定されるパラメーターX及びYが、下記式(1)~(5)を満たす、蓄熱材組成物。
[数1]
X=CA/(CA+W) (P1)
[数2]
Y=NH/(CA+NH+W) (P2)
[数3]
X-51.75>0 (1)
[数4]
52.75-X>0 (2)
[数5]
4.25-Y>0 (3)
[数6]
1.2245X+Y-66.367>0 (4)
[数7]
-2.1569X+Y+110.27>0 (5) - 融点が27℃以下で、かつ25℃以上28℃以下での融解潜熱が165J/g以上である、請求項1に記載の蓄熱材組成物。
- 前記主剤混合物100質量%は、
前記塩化カルシウム6水和物45.0~55.0質量%と、
前記塩化アンモニウム1.0~5.0質量%と、
前記水43.0~50.0質量%とを含む、請求項1又は2に記載の蓄熱材組成物。 - 塩化ストロンチウム6水和物、水酸化ストロンチウム8水和物、水酸化バリウム8水和物、塩化ストロンチウム、水酸化ストロンチウム、水酸化バリウム、水酸化カルシウム、水酸化アルミニウム、黒鉛、アルミニウム、二酸化チタン、ヘクトライト、スメクタイトクレイ、ベントナイト、ラポナイト、プロピレングリコール、エチレングリコール、グリセリン、エチレンジアミン四酢酸、アルキル硫酸ナトリウム、アルキルリン酸ナトリウム、アルキル硫酸カリウム、及びアルキルリン酸カリウムからなる群より選択される少なくとも1種の過冷却抑制剤をさらに含む、請求項1から3のいずれか一項に記載の蓄熱材組成物。
- ケイ酸ナトリウム、水ガラス、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリカルボキシレートポリエーテルポリマー、アクリル酸・マイレン酸共重合体ナトリウム、アクリル酸・スルホン酸系モノマー共重合体ナトリウム、アクリルアミド・ジメチルアミノエチルメタクリラートジメチル硫酸塩共重合物、アクリルアミド・アクリル酸ソーダ共重合物、ポリエチレングリコール、ポリプロピレングリコール、高吸水樹脂(SAP)、カルボキシメチルセルロース(CMC)、CMCの誘導体、カラギーナン、カラギーナンの誘導体、キサンタンガム、キサンタンガムの誘導体、ペクチン、ペクチンの誘導体、デンプン、デンプンの誘導体、コンニャク、寒天、層状ケイ酸塩、及びこれらの物質の複合物質からなる群より選択される少なくとも1種の増粘剤をさらに含む、請求項1から4のいずれか一項に記載の蓄熱材組成物。
- 塩化ナトリウム、塩化カリウム、硝酸ナトリウム、臭化ナトリウム、塩化アンモニウム、臭化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、リン酸アンモニウム、及び尿素からなる群より選択される少なくとも1種の融点降下剤をさらに含む、請求項1から5のいずれか一項に記載の蓄熱材組成物。
- 前記過冷却抑制剤が、水酸化ストロンチウム8水和物又は水酸化ストロンチウムである、請求項4から6のいずれか一項に記載の蓄熱材組成物。
- 前記主剤混合物100質量部と、前記水酸化ストロンチウム8水和物又は水酸化ストロンチウム0.3~1.1質量部とを含む、請求項7に記載の蓄熱材組成物。
- 過冷却抑制添加剤をさらに含む、請求項4から8のいずれか一項に記載の蓄熱材組成物。
- 前記過冷却抑制剤が、水酸化ストロンチウム8水和物であり、
前記過冷却抑制添加剤は、デカン酸、珪藻土、レーヨン、オクタデカン、リン酸モノドデシルナトリウム、1-プロパノール、ポリエステル不織布、ポリエステル繊維、及びアルミナからなる群より選択される1種以上の物質である、請求項9に記載の蓄熱材組成物。 - 前記主剤混合物100質量部と、前記水酸化ストロンチウム8水和物0.3~1.1質量部と、前記過冷却抑制添加剤0.4~1.1質量部とを含む、請求項10に記載の蓄熱材組成物。
- 前記過冷却抑制剤が、水酸化ストロンチウムであり、
前記過冷却抑制添加剤は、オクタデカン、レーヨン、ブロモオクタデカン、1-プロパノール、アルミナ、ポリエステル不織布、2-プロパノール、グリセリン、及びリン酸モノドデシルナトリウムからなる群より選択される1種以上の物質である、請求項9に記載の蓄熱材組成物。 - 前記主剤混合物100質量部と、前記水酸化ストロンチウム0.3~1.1質量部と、前記過冷却抑制添加剤0.05~3.1質量部とを含む、請求項12に記載の蓄熱材組成物。
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