JPH0748565A - Cold-reserving agent - Google Patents

Abstract

PURPOSE:To obtain a cold-reserving agent which does not form lumps on crystallization, is safe, and is excellent in sense to the touch and in cold feeling by mixing a sodium phosphate salt, an ammonium sodium phosphate salt or an ammonium phosphate salt, and water. CONSTITUTION:A cold-reserving agent which utilizes endotherm on dissolution of inorg. salt crystals in water caused by temp. rise near at room temp. is prepd. by mixing a sodium phosphate salt, an ammonium sodium phosphate salt or an ammonium phosphate salt, and water. A pref. sodium phosphate salt used is one mainly comprising disodium hydrogenphosphate or its hydrate; a pref. ammonium sodium phosphate salt or an ammonium phosphate salt used is one mainly comprising ammonium sodium hydrogenphosphate or its salt, otherwise diammonium hydrogenphosphate or its salt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a cooling agent, and more particularly to a cooling agent having excellent cooling performance and tactile sensation.
Cooling agent for obtaining a comfortable and highly safe cooling tool without causing lumps of crystals and causing no discomfort when used to cool the head or affected areas, or tearing the bag. Regarding

[0002]

2. Description of the Related Art Conventionally, ice cubes, water pillows, etc. have been used for a long time for the purpose of cooling the head and the affected area. In addition, recently, a refreshing pillow utilizing the endotherm generated when crystals of inorganic salts dissolve in water as a solvent is being marketed, and sodium sulfate and water or hydrogen phosphate as a cooling agent used for this pillow.
A combination of sodium and water is known (Japanese Utility Model Publication No. 4-21809).

[0003]

However, there are many inconveniences, such as the weight of ice cubes and water pillows are generally large, and it is necessary to prepare ice and cold water for each use.
In addition, a cooling and heating agent that combines sodium sulfate and water or disodium hydrogen phosphate and water is superior to ice-cap and water pillow in terms of simplicity, but once melted and recrystallized, the crystal grains become large. Not only does it feel uncomfortable during use and cause discomfort, but it also has the drawback that if left as it is, the crystals will agglomerate and the bag containing the cooling / heating agent will be broken by impact due to hard crystals. It was

[0004]

[Means for Solving the Problems] The present inventors have studied to solve these problems and obtain a cooling agent which is safe and does not agglomerate at the time of crystallization, and which has an excellent feeling and cooling feeling. As a result of repeating the above, it was found that these problems can be solved by using a combination of sodium phosphates and salts such as sodium ammonium phosphate and ammonium phosphate as inorganic salts that precipitate crystals near room temperature, and reached the present invention. did. That is, the present invention relates to a cooling agent utilizing an endotherm generated when a crystal substance of an inorganic salt dissolves in water as a solvent due to a temperature rise near room temperature, and a sodium phosphate, an ammonium sodium phosphate or an ammonium phosphate salt. And a water-mixing agent, which is a cooling agent. In the cooling agent of the present invention, sodium-containing phosphates and ammonium-containing phosphates are used in combination as inorganic salts for the cooling agent, and these are mixed with water, and sealed and stored in a water-impermeable flat bag or the like. Is used.

Examples of the sodium phosphates used in the present invention include disodium hydrogen phosphate (Na ₂ H).
PO ₄ ), its 12H ₂ O hydrate, etc., sodium dihydrogen phosphate (NaH ₂ PO ₄ ), its 2H ₂ O hydrate, etc.
Examples include trisodium phosphate (Na ₃ PO ₄ ), its 10H ₂ O hydrate, and the like. Among these, those containing disodium hydrogen phosphate and its hydrate as a main component are preferable.

Examples of ammonium phosphate sodium salts or ammonium phosphate salts used in combination with the above sodium phosphate salts include, for example, sodium ammonium hydrogen phosphate (NaNH ₄ HPO ₄ ) and its 4H ₂ O hydrate,
2 ammonium hydrogen phosphate [(NH ₄ ) ₂ HPO ₄ ], ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ), 3 ammonium phosphate [(NH ₄ ) ₃ PO ₄ ], and their 3H ₂ O
Hydrates and the like. Among these, sodium ammonium hydrogenphosphate, diammonium hydrogenphosphate and hydrates thereof are preferred.

The cooling agent is usually prepared by mixing the sodium phosphate and the sodium ammonium hydrogenphosphate or the ammonium phosphate as described above with water, or after heating and dissolving them. , Can be prepared by re-precipitating crystals, but the former method is usually used. It is also possible to mix an acid, an alkali, a salt or the like that reacts in water to generate them and use them as a cooling agent. For example, as a method of producing sodium phosphate salts containing disodium hydrogen phosphate as a main component, a method of neutralizing phosphoric acid with caustic soda or sodium carbonate, and 3 phosphoric acid
Sodium (Na ₃ P ₃ O ₉ ), Trisodium phosphate (N
a ₃ PO ₄ ), sodium dihydrogen phosphate (NaH ₂ P
O ₄ ), sodium pyrophosphate (Na ₄ P ₂ O ₇ ), disodium dihydrogen pyrophosphate (Na ₂ H ₂ P ₂ O ₇ ), sodium metaphosphate [(NaPO ₃ ) n], sodium tripolyphosphate (Na ₅ For example, there is a method of adding phosphoric acid to an aqueous solution of anhydrous sodium phosphate such as P ₃ O ₁₀ ) or a hydrate salt.

Further, as a method of producing an ammonium salt containing ammonium hydrogenphosphate sodium salt as a main component, for example, a method of adding ammonium chloride to an aqueous solution of disodium hydrogenphosphate, ammonium dihydrogenphosphate,
A method of adding caustic soda to an aqueous solution of dibasic ammonium phosphate, anhydrous triammonium phosphate, hydrate salt, etc., a method of producing ammonium phosphate salts from phosphoric acid and aqueous ammonia, and further producing them through the above steps, etc. is there. In these methods, other sodium phosphates or ammonium phosphates may be mixed together at the same time depending on the production conditions, but they can be used as they are as a cooling agent.

The cooling agent according to the present invention is a region where the temperature is relatively low in room temperature, for example, crystals are precipitated at a temperature such as 10 to 25 ° C. and the temperature rises due to body temperature, for example, 20 to 28.
The concentration and mixing ratio of the salts are appropriately determined so that the crystals precipitated at a temperature such as ℃ can be dissolved while generating an endotherm.
The weight of the sodium phosphate and ammonium phosphate sodium salt or the combined salt of ammonium phosphate salt is
Those that exist as an aqueous solution and those that precipitate as crystals are combined, and usually 5 to 6 of the total weight of the cooling / heating agent in terms of anhydride.
It is 0% by weight, preferably 15 to 35% by weight, more preferably 20 to 30% by weight. When the weight of the salt is less than 5% by weight, it becomes difficult to recrystallize at room temperature.
If the amount is larger than the weight%, the amount of crystals becomes too large and the feeling of the cooling agent may be deteriorated.

The ratio of sodium hydrogen phosphate and ammonium phosphate to the sodium phosphate is not particularly limited, but the ratio of Na and NH ₄ groups (Na / NH ₄₎ contained in the entire phosphate in the cooling / heating agent. ) Is a molar ratio, usually 1: 5 to 5: 1, preferably 1: 1 to 5: 1
And the total molar ratio of Na and NH ₄ groups to 1 mole of PO ₄ groups, that is [(Na + NH ₄ ) / PO ₄ ].
Is usually 1: 1.5 to 2.5, preferably 1: 1.8 to
It is set to 1: 2.2. If the balance of the proportions of Na, NH ₄ groups and PO ₄ groups deviates from these ranges too much, the crystal grains may become large or agglomerate.
Further, the pH of the solution may be 10 or more or 4 or less, which may cause a safety problem in handling during manufacturing.

In the present invention, if necessary, other salts may be used in combination with the above-mentioned salts for the purpose of adjusting the amount of crystal precipitation and the melting temperature of the cooling agent.
For example, sodium carbonate, sodium hydrogen carbonate, sodium potassium carbonate, sodium chromium carbonate, sodium scandium carbonate, sodium cerium carbonate, sodium sulfate and hydrates thereof can be used in combination.

In the present invention, it is preferable to add a crystal nucleating agent for the purpose of facilitating the precipitation of crystals.
Crystal nucleating agents include lithium, potassium or alkaline earth metal phosphates, hydroxides and hydrates thereof. Examples of phosphates include potassium phosphates, strontium phosphates, lithium phosphates, calcium phosphates, barium phosphates, magnesium phosphates and hydrates thereof, and examples thereof include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, 3 potassium phosphates, 3 lithium phosphates, 2 lithium hydrogen phosphates, 2 lithium hydrogen phosphates, 2 strontium phosphates, 3 strontium hydrogen phosphates, 2 strontium hydrogen phosphates, 3 calcium phosphates, 2 calcium phosphates, 2 hydrogen phosphates, 2 phosphates 3 magnesium, magnesium hydrogen phosphate, 2 magnesium tetrahydrogen phosphate, 3 barium diphosphate, 4 barium hydrogen phosphate, 4 phosphoric acid
In addition to barium hydrogen and hydrates thereof, pyrophosphates that hydrolyze in water to form these salts are also effective. As the hydroxide,
Examples thereof include strontium hydroxide, calcium hydroxide, lithium hydroxide, barium hydroxide, magnesium hydroxide and hydrates thereof. Of these, potassium phosphates, calcium phosphates, strontium phosphates, calcium hydroxide, strontium hydroxide, and their hydrates are preferable, and potassium dihydrogen phosphate, dipotassium hydrogen phosphate, calcium hydrogen phosphate,
Strontium hydrogen phosphate, strontium hydroxide, hydrates thereof, and the like are particularly preferable. These crystal nucleating agents may be used alone or in combination of two or more kinds.

[0013] By adding and mixing these crystal nucleating agents, crystals are usually in a fine and stable precipitation state. However, when hydroxide is used, after the addition in order to precipitate finer crystals. , Once heated to about 80 ℃,
It is preferable to use by cooling and precipitating crystals. The amount of the crystal nucleating agent is 0.01 to 5% by weight, preferably 0.05 to 3% by weight, based on the total amount of the cooling agent.

In the present invention, a polymer water retention agent is used for the purpose of preventing agglomeration, maintaining a fine crystalline state at all times, providing a soft feeling, and enhancing the safety so that the chemical solution does not splash to the human body even if the bag is torn. Agents, thickeners, polymer flocculants and the like can be added. As the polymer water retention agent, for example, polyacrylic acid, starch-acrylic acid graft copolymer, maleic acid copolymer, polyvinyl alcohol, isobutylene-maleic acid copolymer, and the like, as a thickener, for example, xanthan gum (polysaccharide) ), Carboxymethyl cellulose, sepiolite clay, and the like, as a polymer flocculant, there are cationic type, anionic type, nonionic type, zwitterionic type, etc., for example, polymethacrylic acid ester, polyallylamine, polyacrylamide, chitosan, polyacrylic acid. Examples thereof include soda, acrylamide-sodium acrylate copolymer, polyacrylamide partial hydrolyzate, and polyethylene oxide. These may be used alone or in combination of two or more. Among these, polymeric water retention agents and polysaccharide thickeners are preferable, and in the former, for example, Sunfresh IM-500D, ST-500MPS (manufactured by Sanyo Kasei Co., Ltd.), AQUALIC CS6S, 6HM.
(Manufactured by Nippon Shokubai Co., Ltd.) and other polyacrylic acid-based polymer water retention agents, particularly those in the form of fine powder such as Sunfresh ST-500MPS and Aqualic CS6S. Xanthan gum) and the like are preferable. The addition amount is usually 0.01 to
It is 3% by weight, preferably 0.1 to 2% by weight.

The cooling / heating agent of the present invention is usually sealed and stored in a water-impermeable bag and is mainly used as a refreshing pillow, and can also be used as a cooling bag for cooling an affected area. A synthetic resin film or the like is used as the material for the bag containing the cooling / heating agent, and examples thereof include synthetic resin films such as polyethylene, polypropylene, polyester, nylon, polyvinyl chloride, polyvinylidene chloride, and polyisocyanate, and composite films thereof. , Polyvinyl chloride, nylon and composite films of these are preferable in terms of strength, flexibility, ease of processing and price.

When these are used as a refreshing pillow, the cooling / heating agent is stored in a flat bag, but with a better feeling,
For the purpose of comfortably sleeping and enhancing the fatigue recovery effect, whether the outer surface or one side of the bag made of synthetic resin film should be covered with absorbent cotton, gauze, a non-woven fabric consisting of a water-absorbent fiber layer, or a flocked cloth with a water-absorbent fiber layer. Alternatively, it may be in the form of being stuck together. There is no particular limitation on the size and shape of the flat bag, as long as it has an area of a size that can be applied to various commonly known pillows, for example, a rectangle, a square, a circle, an ellipse. The shape may be any shape depending on the purpose of use and preference. The flat bag containing the cooling / heating agent is used as a refreshing pillow, for example, as it is, or by covering it with a softer cover material, or by storing it in a thick pillow or the like provided with a storage portion such as a pocket. It

The cooling pillow and cooling bag thus obtained are used in a state where a large amount of fine crystals are deposited at a temperature of 10 to 25 ° C. The cooling agent absorbs the heat while cooling the head and the like, and the crystal melts again due to the temperature rise.
A desired temperature such as 0 to 28 ° C. is maintained, and a refreshing feeling is obtained for a long time. And after use 10 ~ 25 ℃
By placing it in a low temperature atmosphere such as above, crystals are precipitated again, so that it can be repeatedly used as it is.

[0018]

【Example】

Example 1 Two colorless semi-transparent soft vinyl chloride films having a thickness of 90 μm and cut into 220 × 240 mm were superposed on each other.
High-frequency welding was performed on each side with a width of 5 mm to produce a flat bag with one side open. In this bag, ion-exchanged water was added to 162 g of disodium hydrogen phosphate and 162 g of sodium ammonium hydrogen phosphate in terms of anhydride, and the total weight was 1300.
The cooling agent obtained as g was stored, and the opening was sealed by high-frequency welding to manufacture a cooling pillow. When this cooling pillow was immersed in a constant temperature water bath at 30 ° C. to dissolve the crystals and then left in a room at 10 ° C. overnight, crystals were precipitated again. The crystals were fine, slurry-like and the entire pillow was soft and had a good feel.

Next, by applying the temperature characteristic test method (JIS S4100) of the disposable paddle, one side of the above-mentioned cooling pillow is brought into close contact with the outer wall of a constant temperature water bath kept at 30 ° C., and the other side is thermocoupled. After a thermometer was attached and the surface was covered with three flannel and securely fixed with tape, the temperature change was measured. As a result, the temperature gradually increased while the crystals gradually dissolved, and it took about 8 hours until the temperature reached from 10 ° C to 25 ° C.
It took a total of 14 hours to rise to 28 ° C,
The comfortable temperature as a refreshing pillow was maintained. This sample was left in a chamber at 10 ° C. again to precipitate crystals, and the state was observed. The crystals were fine and the cooling agent was in the form of a slurry. It was left as it was for one week, but the condition was almost unchanged, and no lumps were observed. As a result of further observation, crystals having a grain diameter of about 3 to 6 mm were partially observed only after 5 days.

Example 2 As the composition of the cooling agent, the cooling agent prepared by adding ion-exchanged water to 240 g of disodium hydrogenphosphate and 78 g of diammonium hydrogenphosphate in terms of anhydride to prepare a total weight of 1300 g was used. A sample of a refreshing pillow was manufactured in the same manner as in Example 1. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystals gradually dissolved, it took about 8 hours to reach 25 ° C. and a total of 14 hours to reach 28 ° C. for a long time. A comfortable temperature was maintained. This sample was left in a chamber at 10 ° C. again to precipitate crystals, and the state was observed. The crystals were fine and the cooling agent was in the form of a slurry. It was left as it was for one week, but the condition was almost unchanged, and no lumps were observed. As a result of further observation, after 7 days, crystals having a grain diameter of about 3 to 6 mm were partially observed for the first time.

Example 3 As the composition of the cooling agent, 200 g of disodium hydrogen phosphate, 36 g of sodium ammonium hydrogen phosphate, in terms of anhydride,
A cooling pillow sample was prepared in the same manner as in Example 1 except that ion-exchanged water was added to 35 g of diammonium hydrogen phosphate to prepare a total weight of 1300 g, and the cooling agent was used. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystal gradually melted, it took about 8 hours until it reached 25 ° C, and a total of 14 hours until it reached 28 ° C. A comfortable temperature was maintained throughout. This sample was left in a chamber at 10 ° C. again to precipitate crystals, and the state was observed. The crystals were fine and the cooling agent was in the form of a slurry. It was left as it was for one week, but the condition was almost unchanged, and no lumps were observed. As a result of further observation, after 5 days, crystals having a grain size of about 4 to 8 mm were partially observed for the first time.

Example 4 As the composition of the cooling and cooling agent, ion-exchanged water was added to a composition obtained by adding 240 g of disodium hydrogen phosphate and 78 g of diammonium hydrogen phosphate and 1 g of strontium hydroxide as a crystal nucleating agent in terms of anhydride. A cooling pillow sample was produced in the same manner as in Example 1 except that the cooling / heating agent prepared as a weight of 1300 g was used. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystal gradually melted, it took about 8 hours until the temperature reached 25 ° C.
A comfortable temperature was maintained for a total of 14 hours until reaching 28 ° C. When this sample was left in a chamber at 10 ° C. again and the state of crystal precipitation was observed, fine needle-like crystals were precipitated and the whole became a slurry. It was left for one week as it was, but the state was almost unchanged, and the same observation was made after 3 months, but the state was hardly changed and no lumps and the like were observed. As a result of further observation, crystals were partially observed with a grain diameter of about 4 to 8 mm only after 15 days.

Example 5 As the composition of the cooling and cooling agent, ion-exchanged water was added to a composition prepared by adding 240 g of disodium hydrogen phosphate and 78 g of diammonium hydrogen phosphate to 2 g of lithium hydroxide as a crystal nucleating agent in terms of an anhydride. A cooling pillow sample was produced in the same manner as in Example 1 except that the cooling / heating agent prepared as a weight of 1300 g was used. Using this sample, a test was conducted under the same conditions as in Example 1, and it was found that the crystals gradually melted and the temperature was 28 ° C. for about 8 hours until the temperature reached 25 ° C.
A comfortable temperature was maintained for a total of 14 hours until the temperature reached. When this sample was allowed to stand in a chamber at 10 ° C. again and the state of crystal precipitation was observed, fine crystals were precipitated and the whole became a slurry. It was left for one week as it was, but the state was almost unchanged, and the same observation was made after 3 months, but the state was hardly changed and no lumps and the like were observed. As a result of continuing the observation, crystals having a grain diameter of about 3 to 6 mm were partially observed only after one month.

Example 6 As the composition of the cooling and cooling agent, 240 g of disodium hydrogen phosphate and 78 g of diammonium hydrogen phosphate added with 2 g of calcium hydrogen phosphate dihydrate as a crystal nucleating agent were added with ion-exchanged water. In addition, a sample was manufactured in the same manner as in Example 1 except that the cooling / heating agent prepared so that the total weight was 1300 g was used. Using this sample, a test was conducted under the same conditions as in Example 1, and it was observed that the crystals gradually melted, while the crystals reached about 25 ° C. for about 8 hours.
A comfortable temperature was maintained for a total of 14 hours until reaching ℃. When this sample was left in a chamber at 10 ° C. again and the state of crystal precipitation was observed, a large number of fine crystals were precipitated and the whole became a slurry. It was left as it was for one week, but the state was almost unchanged, and the same observation was made after 3 months, but the state was almost unchanged, and no lumps and the like were observed. As a result of continuing the observation, crystals having a grain diameter of about 3 to 6 mm were partially observed only after one month.

Example 7 As a composition of a cooling agent, 240 g of disodium hydrogen phosphate, 78 g of diammonium hydrogen phosphate in terms of anhydride, 2 g of calcium hydrogen phosphate dihydrate as a crystal nucleating agent, and Sunfresh IM as a polymer water retention agent A sample was manufactured in the same manner as in Example 1 except that 9 g of -500D (manufactured by Sanyo Kasei Co., Ltd.) was added, and ion-exchanged water was added to make a total weight of 1300 g. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystal gradually melted, it took about 8 hours until the temperature reached 25 ° C.
A comfortable temperature was maintained for a total of 14 hours until reaching 28 ° C. When this sample was left in a room at 10 ° C again and the state of crystal precipitation was observed, a large number of fine crystals were precipitated and the whole became a slightly viscous slurry, which was soft and had a soft feel. was gotten. It was left as it was for one week, but the state was hardly changed, and the same observation was made after 3 months and 6 months, but the state was hardly changed and no lumps and the like were observed. As a result of continuing the observation, crystals having a grain diameter of about 3 to 6 mm were partially observed only after one month.

Example 8 As the composition of the cooling agent, sodium phosphate 12 in terms of anhydride was used.
0 g, 120 g of ammonium dihydrogen phosphate, 2 g of calcium hydrogen phosphate dihydrate as a crystal nucleating agent, and 6 g of Sunfresh ST-500MPS (manufactured by Sanyo Chemical Industry Co., Ltd., fine powder type) as a polymer water retention agent, A sample was manufactured in the same manner as in Example 1 except that ion-exchanged water was added thereto to make the total weight 1300 g. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystals gradually dissolved, it took about 8 hours to reach 25 ° C. and a total of 14 hours to reach 28 ° C. for a long time. A comfortable temperature was maintained. When this sample was left in a room at 10 ° C again and the state of crystal precipitation was observed, a large number of fine crystals were precipitated and the whole became a slightly viscous slurry, which was soft and had a soft feel. was gotten. It was left as it was for one week, but the state was hardly changed, and the same observation was made after 3 months and 6 months, but the state was hardly changed and no lumps and the like were observed. As a result of further observation, crystals having a grain diameter of about 4 to 8 mm were partially observed only after 10 days.

Example 9 As a composition of a cooling and heating agent, 240 g of disodium hydrogen phosphate, 78 g of diammonium hydrogen phosphate in terms of anhydride, 2 g of calcium hydrogen phosphate dihydrate as a crystal nucleating agent, and Sunfresh ST as a polymer water retention agent A sample was prepared in the same manner as in Example 1 except that 9 g of -500 MPS (manufactured by Sanyo Chemical Industry Co., Ltd., fine powder type) was added, and ion-exchanged water was added to make a total weight of 1300 g. Using this sample, a test was conducted under the same conditions as in Example 1. As the crystals gradually dissolved, it took about 8.5 hours until the temperature reached 25 ° C, and a total of 15 hours until the temperature reached 28 ° C. A comfortable temperature was maintained over time. When this sample was left in a room at 10 ° C again and the state of crystal precipitation was observed, a large number of fine crystals were precipitated and the whole became a slightly viscous slurry, which was soft and had a soft feel. was gotten. The sample was left as it was for one week, but the state was hardly changed, and the same observation was made after 3, 6, and 9 months, but the state was hardly changed and no lumps and the like were observed.

Example 10 As a composition of a cooling agent, 240 g of disodium hydrogen phosphate, 78 g of diammonium hydrogen phosphate in terms of anhydride, 2 g of calcium hydrogen phosphate dihydrate as a crystal nucleating agent, and Kelzam (rice, as a thickening agent) Kelco, xanthan gum) 7g
And ion-exchanged water are added to this to obtain a total weight of 1300.
A sample was manufactured in the same manner as in Example 1 except that g was used. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystals gradually dissolved, it took about 8 hours to reach 25 ° C. and a total of 14 hours to reach 28 ° C. for a long time. A comfortable temperature was maintained. When this sample was left in a room at 10 ° C. again and the state of crystal precipitation was observed, many fine crystals were precipitated,
The whole was in the form of a slurry with a slight viscosity, and a soft and soft feeling was obtained. It was left as it was for one week, but the state was almost unchanged, and the same observation was made after 3 months, 6 months and 9 months, but the state was hardly changed and no lumps and the like were observed.

Example 11 As a composition of a cooling agent, 194 g of sodium dihydrogen phosphate, 65 g of sodium hydroxide and 78 g of diammonium hydrogen phosphate were added to 1 g of strontium hydroxide as a crystal nucleating agent in terms of anhydride, and ion exchange was carried out. A cooling pillow sample was manufactured in the same manner as in Example 1 except that a cooling and heating agent having a total weight of 1300 g was added. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystals gradually dissolved, it took about 8 hours to reach 25 ° C. and a total of 14 hours to reach 28 ° C. for a long time. A comfortable temperature was maintained. When this sample was allowed to stand in a chamber at 10 ° C. again and the state of crystal precipitation was observed, fine needle-like crystals were precipitated, and the whole became a slurry. It was left as it was for 1 week, but the state was almost unchanged, and after 3 months, it was observed in the same manner, but the state was almost unchanged, and no lumps or the like were observed. At 4 to 8 mm, some crystals were partially observed.

Example 12 As a composition of a cooling agent, trisodium phosphate 1 in terms of anhydride was used.
Example 2 was repeated except that 2 g of calcium hydroxide was added to 85 g of phosphoric acid, 55 g of phosphoric acid and 78 g of diammonium hydrogen phosphate as a crystal nucleating agent, and ion-exchanged water was added to the mixture to prepare a total weight of 1300 g. Similarly, a sample of a cool pillow was produced. Example 1 using this sample
When the test was conducted under the same conditions as in the above, the temperature was gradually dissolved, and the comfortable temperature was maintained for about 8 hours until reaching 25 ° C and for a total of 14 hours until reaching 28 ° C. When this sample was left in a chamber at 10 ° C. again and the state of crystal precipitation was observed, fine crystals were precipitated, and the whole became a slurry. I left it as it was for a week, but the condition remained almost unchanged, and after 3 months,
When observed in the same manner, the state remained almost unchanged, no lumps and the like were observed, and only after a lapse of one month, crystals having a grain diameter of about 4 to 8 mm were partially observed.

Example 13 As a composition of a cooling agent, 240 g of disodium hydrogen phosphate, 78 g of diammonium hydrogen phosphate in terms of anhydride, 2 g of potassium dihydrogen phosphate as a crystal nucleating agent, and Sunfresh ST-500MPS ( Example 1 except that 9 g of Sanyo Kasei Kogyo Co., Ltd., fine powder type) was added, and ion-exchanged water was added to make a total weight of 1300 g.
A sample was manufactured in the same manner as in. Using this sample, a test was conducted under the same conditions as in Example 1. As the crystals gradually dissolved, it took about 8.5 hours to reach 25 ° C., and a total of 15.5 hours to reach 28 ° C. And a comfortable temperature was maintained for a long time. When this sample was left in a room at 10 ° C again and the state of crystal precipitation was observed, a large number of fine crystals were precipitated, and the whole became a viscous slurry, which was soft and soft. Was obtained. The sample was left as it was for one week, but the state was hardly changed, and the same observation was made after 3, 6, and 9 months, but the state was hardly changed and no lumps and the like were observed.

Example 14 As a composition of a cooling agent, 240 g of disodium hydrogen phosphate, 78 g of diammonium hydrogen phosphate in terms of anhydride, 1 g of calcium hydrogen phosphate dihydrate as a crystal nucleating agent, 1 g of potassium dihydrogen phosphate, polymer Sunfresh S as a water retention agent
A sample was manufactured in the same manner as in Example 1 except that 9 g of T-500 MPS (manufactured by Sanyo Chemical Industry Co., Ltd., fine powder type) was added, and ion-exchanged water was added to make the total weight 1300 g. Using this sample, a test was conducted under the same conditions as in Example 1, and as the crystals gradually melted, it took about 8.5 hours until the temperature reached 25 ° C. for 28 hours.
A comfortable temperature was maintained for a long time of 15.5 hours until the temperature reached ℃. When this sample was left in a room at 10 ° C again and the state of crystal precipitation was observed, a large number of fine crystals were precipitated, and the whole became a viscous slurry, which was soft and soft. Was obtained. It was left for one week as it was, but the state remained almost the same, and it was observed in the same manner after 3 months, 6 months and 9 months.
The condition was almost unchanged, and no lumps were observed.

Comparative Example 1 As the composition of the cooling and cooling agent, ion-exchanged water was added to 324 g of disodium hydrogen phosphate in terms of anhydride, and the total weight was 1300 g.
Samples were manufactured in the same manner as in Example 1 except that When a test was performed using this sample under the same conditions as in Example 1, after about 4 hours, 25 ° C. and 10
After 28 hours, the temperature rose to 28 ° C. When the recrystallized state of this sample was observed in the same manner as in the example, a large number of relatively large crystals having a grain diameter of about 6 to 12 mm were formed. When left alone for one week, the crystals grew larger and became lumps, which could not be crushed just by applying force with fingers.

Comparative Example 2 As the composition of the cooling and cooling agent, sodium sulfate of 3 was calculated as an anhydride.
A sample was manufactured in the same manner as in Example 1 except that ion-exchanged water was added to 80 g to make the total weight 1300 g. When a test was performed using this sample under the same conditions as in Example 1, the temperature rose to 25 ° C. after 2 hours and to 28 ° C. after 6 hours. When the recrystallized state of this sample was observed in the same manner as in Example 1, a larger number of crystal lumps than those in Comparative Example 1 were generated. I tried to crush it by applying force with my hands, but I could not crush it, and when I hit it even more strongly, the bag pierced and the liquid leaked out. Tables 1 and 2 summarize the results of the above Examples and Comparative Examples.

[0035]

[Table 1] Table 1 Examples Examples Inorganic salts Nucleating agents Water retention agents, etc. Cooling continuous fine crystal No. Type Weights Weights Hours Days (g) (g) (Hr) (Day) 1 Na ₂ HPO ₄ 162 − − 14 12 NaNH ₄ HPO ₄ 162 2 Na ₂ HPO ₄ 240 − − 14 14 (NH ₄ ) ₂ HPO ₄ 78 3 Na ₂ HPO ₄ 200 − − 14 12 NaNH ₄ HPO ₄ 36 (NH ₄ ) ₂ HPO ₄ 35 4 Na ₂ HPO ₄ 240 Sr (OH) ₂ 1 14 105 (NH ₄ ) ₂ HPO ₄ 78 5 Na ₂ HPO ₄ 240 LiOH 2 14 120 (NH ₄ ) ₂ HPO ₄ 78 6 Na ₂ HPO ₄ 240 CaHPO ₄ 2 14 120 (NH ₄ ) ₂ HPO ₄ 7 8 7 Na ₂ HPO ₄ 240 CaHPO ₄ 2 14 210 (NH ₄ ) ₂ HPO ₄ 78 ID-500D 9 8 Na ₃ PO ₄ 120 CaHPO ₄ 2 14 190 NH ₄ H ₂ HPO ₄ 120 ST-500M 6 9 Na ₂ HPO ₄ 240 CaHPO ₄ 2 15> 270 (NH ₄ ) ₂ HPO ₄ 78 ST-500M 9 9 10 Na ₂ HPO ₄ 240 CaHPO ₄ 2 14> 270 (NH ₄ ) ₂ HPO ₄ 78 Kerzam 7 11 NaH ₂ PO ₄ 194 Sr (OH) ₂ 1 14 105 NaOH 65 (NH ₄ ) ₂ HPO ₄ 78 12 Na ₃ PO ₄ 185 Ca ( OH) ₂ 2 14 120 H ₃ PO ₄ 55 (NH ₄ ) ₂ HPO ₄ 78 13 Na ₂ HPO ₄ 240 KH ₂ PO ₄ 2 15.5> 270 (NH ₄ ) ₂ HPO ₄ 78 ST-500M 9 14 Na ₂ HPO ₄ 240 KH ₂ PO ₄ 1 15.5> 270 (NH ₄ ) ₂ HPO ₄ 78 CaHPO ₄ 1 ST-500M 9

[0036]

[Table 2] Table 2 Comparative examples Comparative examples Inorganic salts Nucleating agents Water retention agents, etc. Cooling continuation Fine crystal No. Species Weight Species Weight hours Maintenance days (g) (g) (Hr) (Day) 1 Na ₂ HPO ₄ 324 − −10 <72 Na ₂ SO ₄ 380 − −6 <1

[0037]

The cooling agent of the present invention is a combination of sodium phosphate-based salts and ammonium phosphate-based salts, and can prevent the agglomeration of crystals, which is a drawback of the prior art.
It can be used many times. Further, when a crystal nucleating agent, a polymer water retention agent, a thickener, etc. were added, a finer and more stable crystal precipitation state was maintained. Therefore, by applying this cooling agent to a cooling pillow, etc., it has excellent cooling performance and is soft and pleasant to the touch, comfortable and safe, and the crystals do not agglomerate even if left for a long time. , It has become possible to use it repeatedly with peace of mind.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masayuki Fujisawa, 5181 Tamura, Hiratsuka, Kanagawa Prefecture, Hiratsuka Plant, Japan Pionics Co., Ltd. (72) Isao Nagatsu, 5181, Tamura, Hiratsuka, Kanagawa Prefecture, Japan (72) Inventor Mamoru Takahashi 5181 Tamura, Hiratsuka-shi, Kanagawa Japan Pionix Co., Ltd. Hiratsuka factory

Claims (9)

[Claims] 1. A cooling agent utilizing an endotherm produced when a crystalline substance of an inorganic salt is dissolved in water as a solvent due to a temperature rise around room temperature, and a sodium phosphate, an ammonium sodium phosphate or an ammonium phosphate is used. A cooling agent comprising a mixture of salt and water. 2. The cooling agent according to claim 1, wherein the sodium phosphate salt is at least one selected from disodium hydrogen phosphate, sodium dihydrogen phosphate, trisodium phosphate, and hydrates thereof. 3. The sodium ammonium phosphate or ammonium phosphate is at least one selected from sodium hydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate or hydrates thereof. The described cooling agent. _4. The ratio of Na to NH ₄ groups (Na / NH ₄ ) contained in the cooling and heating agent is 1: 5 to 5: 1 in a molar ratio,
In addition, the total molar ratio [(Na + NH ₄ ) / PO ₄ ] of Na and NH ₄ groups to 1 mole of PO ₄ groups is 1: 1.5 to 2.
The cooling / heating agent according to claim 1, which is 5. 5. The cooling / heating agent according to claim 1, wherein the amount of phosphates contained in the cooling / heating agent is 5 to 60% by weight in terms of anhydride. 6. The sodium phosphate salt is disodium hydrogen phosphate or a hydrate thereof, and the ammonium phosphate sodium salt or ammonium phosphate salt is sodium ammonium hydrogen phosphate or diammonium hydrogen phosphate or a hydrate thereof. Item 4. The cooling agent according to item 2 or 3. 7. At least one selected from the group consisting of phosphates, hydroxides and hydrates of lithium, potassium and alkaline earth metals as a crystal nucleating agent is 0.01 to the whole cooling and heating agent. The cooling / heating agent according to claim 1, wherein the cooling / heating agent is added in an amount of about 5% by weight. 8. A crystal nucleating agent is potassium phosphate, calcium phosphate, strontium phosphate, calcium hydroxide,
The cooling agent according to claim 7, which is strontium hydroxide or a hydrate thereof. 9. At least one selected from a polymeric water retention agent, a thickening agent, and a polymeric flocculant is added to the entire cooling / heating agent.
The cooling / heating agent according to claim 1, which is added in an amount of 0.01 to 3% by weight.