JP2021123684A5 - - Google Patents

Description

The present disclosure relates to a method for manufacturing a cold storage material.

Patent Literature 1 discloses a cold storage material in which a clathrate hydrate is formed by cooling. The cold storage material according to sample C-6 disclosed in Patent Document 1 is composed of 0.05 mmol AgI and 19 wt % tetrahydrofuran aqueous solution. The regenerator material according to sample C-6 has a melting point of 4.6 degrees Celsius and a crystallization temperature of minus 7 degrees Celsius.

JP 2018-059676 A

An object of the present disclosure is to provide a method for producing a cold storage material suitable for preserving and refrigerating liquid pharmaceuticals or foods.

A method for manufacturing a cold storage material according to the present disclosure includes:
Tetrahydrofuran , water, and at least one selected from the group consisting _of silver phosphate represented by the chemical formula _Ag3PO4 , silver carbonate represented by the chemical formula _Ag2CO3 , and silver _oxide represented by the chemical formula AgO adding two silver compounds into the container to obtain a mixture ;
a step of stirring the mixture in the container to obtain a cold storage material;
has
The cold storage material has a melting point of 2 degrees Celsius or more and 8 degrees Celsius or less, and the heat storage material has a crystallization temperature of 0 degrees Celsius or more and the melting point or less.

The present disclosure provides a method for manufacturing a cold storage material suitable for preserving and refrigerating liquid pharmaceuticals or foods.

FIG. 1 is a graph showing characteristics of a cold storage material during cold storage. FIG. 2 is a graph showing the characteristics of the cold storage material during cooling. FIG. 3 shows a schematic diagram of a cooler box 100 according to a second embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

(First embodiment)
FIG. 1 is a graph showing characteristics of a cold storage material during cooling. In FIG. 1, the horizontal and vertical axes indicate time and temperature, respectively.

The cold storage material according to the first embodiment is cooled. See section A included in FIG. Unlike the case of general liquids, as is well known in the technical field of cold storage materials, even if the temperature of the cold storage material reaches its melting point due to the cooling of the cold storage material, the cold storage material does not solidify. Cool down. See interval B included in FIG. In the supercooled state, the cold storage material is liquid.

The cold storage material then begins to crystallize spontaneously. As it crystallizes, the cold storage material releases heat of crystallization which is almost equal to latent heat. As a result, the temperature of the cold storage material begins to rise. See interval C included in FIG. In this specification, the temperature at which the cold storage material starts to spontaneously crystallize is referred to as "crystallization temperature".

ΔT represents the difference between the melting point and the crystallization temperature of the cold storage material. ΔT may also be referred to as the “degree of subcooling”. Crystallization of the cold storage material in a supercooled state turns the cold storage material into a semi-class hydrate (see, for example, Patent Document 2). Here, the clathrate hydrate refers to a crystal formed by water molecules forming cage-like crystals by hydrogen bonding, and substances other than water being wrapped in the cage-like crystals. A semi-class hydrate is a crystal formed by guest molecules participating in a hydrogen bond network of water molecules. The concentration at which water molecules and guest molecules form a hydrate in just the right amount is called the harmonic concentration. Generally, hydrates are often used near the harmonic concentration.

After the crystallization is completed and the heat of crystallization of the cold storage material is released, the temperature of the cold storage material gradually decreases to become equal to the ambient temperature. See section D included in FIG.

The crystallization temperature is lower than the melting point of the cold storage material. The melting point of the cold storage material can be measured using a differential scanning calorimeter (which may also be referred to as "DSC"), as is well known in the cold storage material art.

FIG. 2 is a graph showing the characteristics of the cold storage material during heating. In FIG. 2, the horizontal and vertical axes indicate time and temperature, respectively. During section E, the temperature of the cold storage material is maintained at a temperature equal to or lower than the crystallization temperature. For example, while the lid of the cooler box is closed, the temperature inside the cooler box is set below the crystallization temperature so that the temperature of the cold storage material placed inside the cooler box is maintained below the crystallization temperature. ing.

Next, the cold storage material is gradually warmed. See section F included in FIG. For example, when the lid of the cooler box is opened (or opened to contain food) at the end of section E (that is, the beginning of section F), the temperature inside the cooler box gradually increases.

When the temperature of the cold storage material reaches the melting point of the cold storage material, the temperature of the cold storage material is maintained near the melting point of the cold storage material. See section G included in FIG. In the unlikely event that there is no cold storage material, the temperature inside the cooler box rises continuously as shown in section Z included in FIG. On the other hand, when there is a cold storage material, the temperature inside the cooler box is maintained near the melting point of the cold storage material for a certain period of time in section G. In this way, the cold storage material exhibits a cold storage effect. At the end of section G, the crystals of the cold storage material melt and disappear. As a result, the cold storage material is liquefied.

After that, the temperature of the liquefied cold storage material rises to become equal to the ambient temperature. See interval H included in FIG.

The cold storage material can be cooled and reused.

For a cold storage material suitably used for a cooler box that can contain liquid medicine or food, the following conditions (I) and (II) must be satisfied.
Condition (I) The cold storage material has a melting point of 2 degrees Celsius or higher and 8 degrees Celsius or lower. For example, the cold storage material should have a melting point of 3 degrees Celsius or higher and 7 degrees Celsius or lower.
Condition (II) The cold storage material has a crystallization temperature of 0°C or higher and the melting point or lower.

The reason for condition (I) is that the inside of the cooler box should be maintained at approximately 2 degrees Celsius or higher and 8 degrees Celsius or lower for the preservation of liquid medicines and foods. If the temperature inside the cooler box is maintained below 0 degrees Celsius, the liquid medicine and food may deteriorate because the water contained inside the liquid medicine and food turns into ice. On the other hand, should the temperature inside the cooler box remain above 8 degrees Celsius, the cooler box is not functioning.

The reason for condition (II) is to increase the efficiency in the section (that is, section B shown in FIG. 1) where the cold storage material is cooled for the purpose of obtaining the function of the cold storage material. Hereinafter, this efficiency will be referred to as the "crystallization efficiency". As the crystallization temperature decreases, the crystallization efficiency decreases. As is clear from FIG. 1 (especially section B in FIG. 1), for example, a cold storage material having a crystallization temperature of minus 18 degrees Celsius (hereinafter referred to as "minus 18 cold storage material") for the purpose of obtaining the function of a cold storage material ), it is necessary to cool the cold storage material in a freezer maintained at a temperature lower than minus 18 degrees Celsius (eg, minus 20 degrees Celsius). On the other hand, for example, in order to cool a cold storage material having a crystallization temperature of minus 1 degree Celsius (hereinafter referred to as "minus 1 cold storage material") for the purpose of obtaining the function of the cold storage material, the temperature is lower than -1 degree Celsius. A cold storage material is cooled in a freezer maintained at a low temperature. The energy required to cool the minus 1 regenerator material is less than the energy required to cool the minus 18 regenerator material. Therefore, the higher the crystallization temperature, the better the crystallization efficiency.

In this technical field, the heat of fusion is also called the latent heat.

To avoid confusion, "Kelvin" is used herein for the degree of supercooling ΔT. For example, the inventor of the present invention expresses that "the degree of supercooling ΔT is n Kelvin or less". Needless to say, n is a real number. The description "degree of supercooling ΔT≦5 Kelvin" means that the difference between the crystallization temperature and the melting point of the cold storage material is 5 Kelvin or less. On the other hand, in this specification, "Celsius" is used for temperature. For example, we write that "the crystallization temperature is 5 degrees Celsius (ie, 5°C)."

The cold storage material according to the first embodiment is
tetrahydrofuran,
Water and _at least one silver compound selected from the group consisting of silver phosphate represented by the chemical formula _Ag3PO4 , silver carbonate represented by the chemical formula _Ag2CO3 , and silver oxide represented by the chemical formula AgO _. contains

As demonstrated in Examples described later, the cold storage material according to the first embodiment has a melting point of 2 degrees Celsius or more and 8 degrees Celsius or less. Therefore, the cold storage material according to the first embodiment is suitably used for preserving liquid pharmaceuticals and foods.

As demonstrated in Examples described later, the cold storage material according to the first embodiment has a crystallization temperature of 0 degrees Celsius or higher. On the other hand, as explained in the prior art section, the cold storage material according to sample C-6 of Patent Document 1 has a crystallization temperature of minus 7 degrees Celsius. Therefore, the cold storage material according to the first embodiment has high crystallization efficiency. In other words, the energy required in the zone B where the cold storage material according to the first embodiment is cooled is smaller than that of the cold storage material according to sample C-6 of Patent Document 1.

As is clear from FIG. 1, the crystallization temperature is below the melting point.

The cold storage material according to the first embodiment is selected from the group consisting of silver phosphate represented by the chemical formula _Ag3PO4 , silver carbonate represented by the chemical formula _Ag2CO3 , and silver oxide represented by the chemical formula _{AgO .} It contains at least one silver compound . As demonstrated in the comparative examples below, when other silver compounds (for example, silver iodide, silver bromide, or silver chloride) are used in place of these three silver compounds, crystals The curing temperature is significantly lowered. Similarly, in place of these three silver compounds, other metal salts such as titanium oxide, vanadium oxide, iron oxide, nickel oxide, manganese oxide, or zinc oxide can be used, as demonstrated in the comparative examples below. ) is also used, the crystallization temperature is significantly lowered.

As long as the cold storage material according to the first embodiment has a melting point of 2 degrees Celsius or more and 8 degrees Celsius or less and a crystallization temperature of 0 degrees Celsius or more and the melting point or less, in the cold storage material of the first embodiment, tetrahydrofuran is added to water. is not limited. As an example, the molar ratio is 5% or more and 7% or less. It is known that when a regenerator material having a molar ratio of tetrahydrofuran to water of 1/17 is cooled, crystals of water and tetrahydrofuran are formed without excess or deficiency of water or tetrahydrofuran.

As demonstrated by Examples 1A to 3D, in the cold storage material of the first embodiment, the molar ratio of silver compound to water is not limited. As an example, the molar ratio is 2.64×10 ⁻⁸ or more and 3.70×10 ⁻⁴ or less.

The cold storage material according to the first embodiment has a melting point of 2° C. or more and 8° C. or less and a crystallization temperature of 0° C. or more and the melting point or less. It may contain an agent.

Examples of additives are supercooling inhibitors, thickeners, and preservatives.

The cold storage material according to the first embodiment may contain no additive. In other words, the cold storage material according to the first embodiment may be composed of tetrahydrofuran, water, and the silver compound.

The cold storage material according to the first embodiment can be produced by mixing tetrahydrofuran, water and the silver compound.

(Second embodiment)
A cooler box according to the second embodiment will be described below.

FIG. 3 shows a schematic diagram of a cooler box 100 according to a second embodiment.

The cooler box 100 comprises an insulated box 101 and an insulated lid 102 consisting of a bottom (not shown) and sides.

In at least one interior selected from the group consisting of the inner bottom surface of the insulation box 101, the inner side surface of the insulation box 101, and the inner surface (i.e., the lower surface) of the insulation lid 102, according to the first embodiment A cold storage material is provided. In FIG. 3, a cold storage material pack 110 containing the cold storage material according to the first embodiment is provided so as to be in contact with each of the four inner side surfaces of a heat insulating box 101 having a rectangular parallelepiped shape.

The cold storage material according to the first embodiment may be provided in at least one selected from the group consisting of the inside of the bottom of the heat insulation box 101 , the inside of the side of the heat insulation box 101 , and the inside of the heat insulation lid 102 . The cold storage material according to the first embodiment is the space inside the cooler box 100 (that is, the space formed by the inner bottom surface of the heat insulating box 101, the inner side surface of the heat insulating box 101, and the inner surface of the heat insulating lid 102). Inside, the cold storage material according to the first embodiment may be enclosed so as to be placed in the form of a cold storage material pack 110 .

The cold storage material according to the first embodiment may be provided in at least one interior selected from the group consisting of the side surface of the heat insulation box, the heat insulation lid of the heat insulation box, and the heat insulation box itself. Also in this case, the cold storage material according to the first embodiment may be provided in the form of the cold storage material pack 110 .

It is desirable that at least one selected from the group consisting of medicines and foods is placed inside the heat insulating box 101 . In FIG. 3, inside the insulation box 101, the medicine 120 is placed. Examples of pharmaceuticals are liquid pharmaceuticals. An example of a liquid pharmaceutical product is a vaccine. In order to maintain the quality of the vaccine when it is transported, it is required that the vaccine be stored at a temperature of 2°C or higher and 8°C or lower. The cooler box according to the second embodiment is suitable for carrying vaccines because the cold storage material according to the first embodiment has a melting point of 2 degrees Celsius or more and 8 degrees Celsius or less.

(Example)
The invention is explained in more detail with reference to the following examples.

In this example, silver phosphate is represented by the chemical formula Ag ₃ PO ₄ . Silver phosphate was purchased from Mitsuwa Chemicals Co., Ltd.
In this example, silver carbonate is represented by _the chemical formula _Ag2CO3 . Silver carbonate was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.
In this example, silver oxide is represented by the chemical formula AgO. In other words, as used herein, silver oxide is silver(II) oxide rather than silver(I) oxide represented by the chemical formula _Ag2O . Silver oxide was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.
In the present examples, tetrahydrofuran is abbreviated as "THF". THF was purchased from Tokyo Chemical Industry Co., Ltd.

(Example 1A)
(Manufacturing method of cold storage material)
First, the reagents shown in Table 1 below were added to a screw tube with a capacity of 60 milliliters to obtain a mixture. The mixture was sufficiently stirred in the screw tube to obtain a cold storage material according to Example 1A.
(Table 1)
0.0419 grams of silver phosphate (equivalent to 1 x 10 ^-4 moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)

Screw tubes were glass tubes with screwed caps.

(Measurement of melting point and crystallization temperature)
A screw tube containing the cold storage material (approximately 6 grams) of Example 1A was placed inside a constant temperature bath (trade name: SU-241, manufactured by Espec Co., Ltd.). A thermocouple was attached to the screw tube, and the temperature inside the screw tube was observed. The thermostat was maintained at 20 degrees Celsius for 2 hours. The temperature of the thermostat was then lowered at a rate of 1 degree Celsius/minute. After the bath temperature reached 4 degrees Celsius, the bath was maintained at 4 degrees Celsius for 30 minutes.

The temperature of the constant temperature bath was then lowered from 4 degrees Celsius to minus 20 degrees Celsius at a rate of 1 degree Celsius/24 hours. The temperature of the cold storage material according to Example 1A placed in the constant temperature bath was recorded using a thermocouple and a data logger (manufactured by Keyence Corporation, trade name: NR-600). From the temperature of the regenerator material after the temperature of the regenerator material rises rapidly (see zone C in FIG. 1) and the melting point (explained in the next paragraph), the crystallization temperature of the regenerator material according to Example 1A is calculated. was done.

The cold storage material according to Example 1A placed in a constant temperature bath was maintained at minus 20 degrees Celsius for 3 hours. The temperature of the thermostat was then increased at a rate of 1 degree Celsius/minute. A differential scanning calorimeter (which may also be referred to as "DSC") was used to measure the melting point of the regenerator material according to Example 1A. As a result, the melting point of the cold storage material according to Example 1A was 4.5 degrees Celsius.

(Example 1B)
In Example 1B, the reagents shown in Table 2 below were used in place of the reagents shown in Table 1, and a screw tube with a volume of 110 milliliters was used instead of a screw tube with a volume of 60 milliliters. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 2)
0.010 grams of silver phosphate (equal to 2.39 x 10 ^-5 moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Example 1C)
In Example 1C, the reagents shown in Table 3 below were used in place of the reagents shown in Table 1, and a screw tube with a volume of 110 milliliters was used instead of a screw tube with a volume of 60 milliliters. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 3)
0.001 grams of silver phosphate (equal to 2.39 x 10 ^-6 moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Example 1D)
In Example 1D, the reagents shown in Table 1 were mixed with the reagents shown in Table 4 below, and a screw tube with a capacity of 110 ml was substituted for a screw tube with a capacity of 60 ml. An experiment similar to that of Example 1A was performed, except that it was used. The results of the experiment are shown in Table 27.
(Table 4)
Regenerator according to Example 1C 5.00 grams THF 18.117 grams (equivalent to about 0.251 moles)
76.883 grams of pure water (equivalent to about 4.27 moles)

(Example 2A)
In Example 2A, the same experiment as in Example 1A was performed, except that the reagents shown in Table 5 below were used in place of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 5)
0.0276 grams of silver carbonate (equal to 1.00×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)

(Example 2B)
In Example 2B, the reagents shown in Table 6 below were used in place of the reagents shown in Table 1, and a screw tube with a volume of 110 milliliters was used instead of a screw tube with a volume of 60 milliliters. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 6)
0.01 grams of silver carbonate (equal to 3.63×10 ⁻⁵ moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Example 2C)
In Example 2C, the reagents shown in Table 7 below were used in place of the reagents shown in Table 1, and a screw tube with a volume of 110 milliliters was used instead of a screw tube with a volume of 60 milliliters. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 7)
0.001 grams of silver carbonate (equal to 3.63×10 ⁻⁶ moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Example 2D)
In Example 2D, the reagents shown in Table 1 were mixed with the reagents shown in Table 8 below, and a screw tube with a capacity of 110 milliliters was substituted for a screw tube with a capacity of 60 milliliters. An experiment similar to that of Example 1A was performed, except that it was used. The results of the experiment are shown in Table 27.
(Table 8)
Regenerator according to Example 2C 20.00 grams THF 15.257 grams (equivalent to about 0.212 moles)
64.743 grams of pure water (equivalent to about 3.60 moles)

(Example 3A)
In Example 3A, the same experiment as in Example 1A was performed, except that the reagents shown in Table 9 below were used in place of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 9)
0.0124 grams of silver oxide (equivalent to 1.00×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)

(Example 3B)
In Example 3B, the reagents shown in Table 10 below were used in place of the reagents shown in Table 1, and a screw tube with a volume of 110 milliliters was used instead of a screw tube with a volume of 60 milliliters. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 10)
0.01 grams of silver oxide (equal to 8.07×10 ⁻⁵ moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Example 3C)
In Example 3C, the reagents shown in Table 11 below were used in place of the reagents shown in Table 1, and a screw tube with a volume of 110 milliliters was used instead of a screw tube with a volume of 60 milliliters. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 11)
0.001 grams of silver oxide (equal to 8.07×10 ⁻⁶ moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Example 3D)
In Example 3D, the reagents shown in Table 1 were mixed with the reagents shown in Table 12 below, and a screw tube with a capacity of 110 milliliters was used instead of a screw tube with a capacity of 60 milliliters. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 12)
Regenerator according to Example 3C 20.0 grams THF 15.257 grams (equivalent to about 0.212 moles)
64.743 grams of pure water (equivalent to about 3.60 moles)

(Reference example 1A)
In Reference Example 1A, the same experiment as in Example 1A was performed except that the reagents shown in Table 13 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 13)
0.0127 grams of silver fluoride (equal to 1.00×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)

(Reference example 1B)
In Reference Example 1B, the reagents shown in Table 14 below were used instead of the reagents shown in Table 1, and the screw tube with a capacity of 110 ml was used instead of the screw tube with a capacity of 60 ml. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 14)
0.01 grams of silver fluoride (equal to 7.88×10 ⁻⁵ moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Reference example 1C)
In Reference Example 1C, the reagents shown in Table 15 below were used in place of the reagents shown in Table 1, and a screw tube with a capacity of 110 ml was used instead of a screw tube with a capacity of 60 ml. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 15)
0.001 grams of silver fluoride (equal to 7.88×10 ⁻⁶ moles)
THF 19.071 grams (equivalent to about 0.264 moles)
80.929 grams of pure water (equal to about 4.50 moles)

(Reference example 1D)
In Reference Example 1D, the reagents shown in Table 1 were mixed with the reagents shown in Table 16 below, and a screw tube with a capacity of 110 ml was used instead of a screw tube with a capacity of 60 ml. A similar experiment to Example 1A was performed, except that the The results of the experiment are shown in Table 27.
(Table 16)
Cold storage material according to Reference Example 1C 50.0 grams THF 9.535 grams (equivalent to about 0.132 moles)
40.465 grams of pure water (equal to about 2.25 moles)

(Reference example 2)
In Reference Example 2, the same experiment as in Example 1A was performed except that the reagents shown in Table 17 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 17)
0.0419 grams of silver phosphate (equivalent to 1 x 10 ^-4 moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
5.407 grams of heavy water (equivalent to about 0.270 moles)
Note that in Reference Example 2, the water was heavy water.

(Comparative example 1)
In Comparative Example 1, the same experiment as in Example 1A was performed except that the reagents shown in Table 18 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 18)
0.0235 grams of silver iodide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Silver iodide was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.

(Comparative example 2)
In Comparative Example 2, the same experiment as in Example 1A was performed, except that the reagents shown in Table 19 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 19)
0.0188 grams of silver bromide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Silver bromide was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.

(Comparative Example 3)
In Comparative Example 3, the same experiment as in Example 1A was performed, except that the reagents shown in Table 20 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 20)
0.0143 grams of silver chloride (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Silver chloride was purchased from Fujifilm Wako Pure Chemical Co., Ltd.

(Comparative Example 4)
In Comparative Example 4, the same experiment as in Example 1A was performed, except that the reagents shown in Table 21 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 21)
0.008 grams of titanium oxide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Titanium oxide was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.

(Comparative Example 5)
In Comparative Example 5, the same experiment as in Example 1A was performed, except that the reagents shown in Table 22 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 22)
0.0182 grams of vanadium oxide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Vanadium oxide was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.

(Comparative Example 6)
In Comparative Example 6, the same experiment as in Example 1A was performed except that the reagents shown in Table 23 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 23)
0.0160 grams of iron oxide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Iron oxide was purchased from Fujifilm Wako Pure Chemical Co., Ltd.

(Comparative Example 7)
In Comparative Example 7, the same experiment as in Example 1A was performed except that the reagents shown in Table 24 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 24)
0.0074 grams of nickel oxide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Nickel oxide was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.

(Comparative Example 8)
In Comparative Example 8, the same experiment as in Example 1A was performed, except that the reagents shown in Table 25 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 25)
0.0071 grams of manganese oxide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Manganese oxide was purchased from Fujifilm Wako Pure Chemical Industries, Ltd.

(Comparative Example 9)
In Comparative Example 9, the same experiment as in Example 1A was performed except that the reagents shown in Table 26 below were mixed instead of the reagents shown in Table 1. The results of the experiment are shown in Table 27.
(Table 26)
0.0081 grams of zinc oxide (equal to 0.1×10 ⁻⁴ moles)
THF 1.144 grams (equivalent to about 0.0159 moles)
4.856 grams of pure water (equivalent to about 0.270 moles)
Zinc oxide was purchased from Fujifilm Wako Pure Chemical Co., Ltd.

The cold storage materials according to Examples 1A, 2A, and 3A, Reference Example 1A, Reference Example 2, and Comparative Examples 1-9 had a volume of approximately 6 milliliters. The cold storage materials according to Examples 1B-1D, Examples 2B-2D, Examples 3B-3D, and Reference Examples 1B-1D had a volume of approximately 100 milliliters.

As is clear from Examples 1A to 3D, the cold storage material containing THF, water, and at least one silver compound selected from the group consisting of silver phosphate, silver carbonate, and silver oxide was It has a melting point of 4.5°C and a crystallization temperature of 1°C to 2°C.

On the other hand, as is clear from Comparative Examples 1 to 3, the cold storage material containing THF, water, and silver halide (excluding silver fluoride) has a melting point of 4.5 degrees Celsius. It has a crystallization temperature of -7 degrees Celsius or less.

As is clear from Comparative Examples 4 to 9, the cold storage material containing THF, water, and metal oxides (excluding silver oxide) has a melting point of 4.5 degrees Celsius, but a melting point of -8 degrees Celsius. It has a crystallization temperature of less than

As described above, the cold storage materials according to Examples 1A to 3D have higher crystallization temperatures than the cold storage materials according to Comparative Examples 1 to 4. Therefore, the cold storage materials according to Examples 1A to 3D are It has a higher crystallization efficiency than the cold storage materials according to Comparative Examples 1 to 4.

As is clear from the comparison of Examples 1A to 3D, the content of the silver compound in the cold storage material does not affect the crystallization temperature.

The cold storage material according to the present disclosure can be used for cooler boxes suitable for storing and refrigerating liquid pharmaceuticals or foods.

100 cooler box 101 heat insulation box 102 heat insulation lid 110 cold storage material pack 120 medicine

Claims (6)

Tetrahydrofuran , water , and at least one selected from the group consisting of silver phosphate represented by the chemical formula Ag ₃ PO ₄ , silver carbonate represented by the chemical formula Ag ₂ CO ₃ , and silver oxide represented by the chemical formula AgO. adding a silver compound into the container to obtain a mixture;
a step of stirring the mixture in the container to obtain a cold storage material;
A method for manufacturing a cold storage material having
The cold storage material has a melting point of 2 degrees Celsius or more and 8 degrees Celsius or less, and the heat storage material has a crystallization temperature of 0 degrees Celsius or more and the melting point or less.
manufacturing method .
The manufacturing method according to claim 1,
wherein the silver compound is the silver phosphate;
manufacturing method .
The manufacturing method according to claim 1,

wherein the silver compound is the silver carbonate;
manufacturing method .
The manufacturing method according to claim 1,
wherein the silver compound is the silver oxide;
manufacturing method .
The production method according to any one of claims 1 to 4,
The molar ratio of the tetrahydrofuran to the water is 0.05 or more and 0.07 or less.
manufacturing method .
The production method according to any one of claims 1 to 5,
the molar ratio of the silver compound to the water is 2.64×10 ⁻⁸ or more and 3.70×10 ⁻⁴ or less;
manufacturing method .