JP3479109B2 - Thermal storage material composition and method for producing the same - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to air conditioning and cooling of buildings and the like.
Composition for latent heat storage material used and method for producing the same
Related. [0002] The condition to be provided as a heat storage material is a heat storage amount.
Large, operating at a given temperature level, long term
Stable, inexpensive, non-toxic,
And non-corrosiveness. Satisfy these conditions
Phase-change hydrated salts are the best considered
But sodium sulfate decahydrate is a typical one
It is. [0003] Sodium sulfate decahydrate has a melting point of 32 ° C.
And has a latent heat of 60 cal / g.
Attempt to use it as a material in conjunction with this in 1952
Sodium tetraborate decahydrate (Na
_Two B _Four O ₇ ・ 10H _Two O) proved to be effective
Since then, many have been considered to date. [0004] The problem encountered in the practical application study is that sulfur
Sodium dodecahydrate shows anharmonic melting
You. That is, anhydrous sodium sulfate is generated during melting,
Settles to the bottom. When cooled, a table of the deposited anhydrous salts
The face layer is condensed to 10-hydrate, but the inside remains as anhydrous salt
I do. Heat storage because residual anhydrous salts do not participate in phase change
The amount will be reduced. To solve this, anhydrous salt
Is to disperse and maintain in the liquid without settling to the bottom of the liquid.
Various studies have been made. They are inorganic or organic
Sedimentation by thickening with additives of porous polymer
It is a method to prevent. For example, Japanese Patent Publication No. 55-501180
As described in JP-A-53-34687,
Attempts have been made to use some inorganic compounds, but not necessarily
Sufficient anti-settling effect was not achieved. Further, polyacryl is used as the organic polymer.
Using a water-soluble polymer such as sodium acid or a cross-linkable polymer
Are disclosed in Japanese Patent Publication No. 57-30873 and Japanese Patent Publication No.
-48027, JP-A-58-132075 and
And JP-A-59-102977.
However, these methods have long-term stability aspects.
But it was not always enough. [0007] JP-A-60-203687 discloses a
In a glass-based thermal storage agent composition, a sodium-based antifoaming agent
Heat by adding water containing water and chelating agent
There has been proposed a method for suppressing the deterioration of the metal. This method
In other words, the co-existence of silicon-based defoamer and chelating agent
Is essential, and if both are missing, 500
A decrease in heat storage after the cycle is observed. Further, a nucleating agent and a surfactant are added to the latent heat type heat storage material.
By adding a humectant and temporarily bringing the heat storage material into a molten state.
There is a proposal for a heat storage material in which the nucleating agent is evenly dispersed.
(JP-A-62-297381). This includes the interface
Addition of activator prevents sedimentation of nucleating agent and uniform dispersion
Therefore, solidification occurs uniformly and the flow of the heat storage agent melt
It is stated that workability will not be impaired because mobility is not impaired.
Have been. However, nucleating agents dispersed in this way
Is maintained dispersed by electrostatic repulsion by surfactant
For months or years of long-term use.
Maintains uniform dispersion of nucleating agent
It is difficult. Therefore, the present inventors first wrote an unsaturated carboxylic acid.
Selected from acids, organic unsaturated sulfonic acids and their salts
Polymerized with at least one monomer and a polyfunctional monomer.
By using the crosslinked polymer obtained by
Heat storage material composition that does not decrease in heat storage
(Japanese Patent Application Laid-Open No. 62-25188).
No.). On the other hand, in a heat storage material for air conditioning and cooling,
Has been put to practical use since its long history of ice storage. This
It utilizes the large latent heat of melting of ice (80 cal / g)
Things. However, it is necessary to prepare ice at -10 ° C.
It is necessary to cool below, for which a special refrigerator
Is necessary, and the initial capital investment is expensive.
There is a point. A heat storage material containing sodium sulfate as a main material.
Now, adjust the melting point to lower the melting point to around 10 ° C.
Agents have been studied. U.S. Pat. No. 4,689,16
In No. 4, per mole of sodium sulfate decahydrate,
3/4 to 6/4 mol of ammonium chloride, potassium chloride 1
/ 5 to 1/4 mole of a composition with thixotropic
Systems have been proposed in which additives and nucleating agents are added. This
Has a melting point of 50 ° F. (10 ° C.) or less and a heat of fusion of 38
~ 42 BTU / lb (21-23 cal / g)
Has been described. However, this system has a difference between the melting point and the freezing point.
Separation is large and it is necessary to cool to 3 ° C or less for coagulation.
Problem. SUMMARY OF THE INVENTION The present invention relates to
It is intended to solve the problems of the existing technology. sand
That is, the present invention relates to a general-purpose refrigerator used in air conditioning and cooling.
In the operating temperature range (6 to 14 ° C)
Heat storage agent composition that occurs and does not decrease the heat storage amount for a long period of time
It provides things. [0013] The present invention provides the following.
It is. 1. (1) 1 mol of sodium sulfate (anhydrous equivalent)
1.5 to 2.5 mol of ammonium chloride, 10 to 2 water
85.0 to 99.5 parts by weight of an inorganic salt composition containing 7 mol,
(2) 0.5 to 15.0 parts by weight of a water-swellable crosslinked polymer,
(3) Surfactant having a polyoxyalkylene chain
It is characterized by containing from 0.01 to 5.0 parts by weight as a main component.
Heat storage material composition. 2. (1) 1 mol of sodium sulfate (anhydrous equivalent)
1.7 to 2.2 mol of ammonium chloride, water 10 to 2
90.0 to 99.5 parts by weight of an inorganic salt composition containing 7 mol,
(2) 0.5 to 10.0 parts by weight of a water-swellable crosslinked polymer,
(3) Surfactant having polyoxyethylene chain 0.0
Characterized in that it contains 1 to 5.0 parts by weight as a main component.
Heat storage material composition. 3. (1) Sodium sulfate (anhydrous equivalent)
1.5 to 2.5 mol of ammonium chloride per mol,
85.0 to 99. an inorganic salt composition containing 10 to 27 mol of water.
5 parts by weight, (2) water-soluble acrylic polymer 0.5 to 15.
0 parts by weight, (3) an interface having a polyoxyalkylene chain
Activator contains 0.01 to 5.0 parts by weight as a main component
A heat storage material composition comprising: 4. Sodium sulfate, ammonium chloride,
An unsaturated carboxylic acid, in the presence of water, and a surfactant,
Organic unsaturated sulfonic acids and their salts and acrylics
At least one monomer selected from amides and polyfunctionality
Characterized by polymerizing a monomer with a polymerization initiator
The method for producing a heat storage material composition according to the above item (1). 5. Sodium sulfate, ammonium chloride,
Water and surfactants having polyoxyethylene chains
In the presence of unsaturated carboxylic acids, organic unsaturated sulfonic acids and
And at least one monomer selected from these salts
Polymerizing a polyfunctional monomer with a polymerization initiator
The method for producing a heat storage material composition according to the above item (2), wherein
Law. 6. Sodium sulfate, ammonium chloride,
Water and surfactants having polyoxyethylene chains
In the presence of unsaturated carboxylic acids, organic unsaturated sulfonic acids and
And at least one monomer selected from these salts,
Acrylamide and polyfunctional monomer with polymerization initiator
Item (2), wherein the polymerization is carried out by using
A method for producing a heat storage material composition. [7] Sodium sulfate, ammonium chloride,
Water and surfactants having polyoxyethylene chains
Polymerization of acrylamide and polyfunctional monomer in the presence
The above item (2), wherein the polymerization is carried out using an initiator.
A method for producing the heat storage material composition according to the above. In the present invention, the raw material sodium sulfate
Is anhydrous sodium sulfate or sodium sulfate decahydrate
Can be used. Ammonium chloride lowers melting point
And the amount used is sodium sulfate
(Equivalent to anhydride) 1.5 to 2.5 mol per mol, preferably
Preferably, it is 1.7 to 2.2 mol. Less than 1.5 moles
Is not enough to lower the melting point.
Also has no effect of lowering the melting point. To adjust the melting point,
Thorium, potassium chloride, sodium nitrate, potassium nitrate
, Magnesium nitrate, etc.
Can also be added. The amount of water used is sodium sulfate (anhydrous
Calculation) 1 to 10 mol to 27 mol, preferably 15 to 1 mol.
２４24 mol. Less than 10 moles of sodium sulfate
It is preferable because the amount of condensate decreases and the amount of stored heat decreases.
If more than 27 mol, dilute sodium sulfate
The effect is so great that it lowers the amount of stored heat.
Not good. The water-swellable crosslinked polymer used in the present invention
Is a polymer having a three-dimensional network structure and a phase with water.
Swells by interaction to form a so-called hydrogel
I mean Among the hydrogels, a polymer electrolyte is used as a raw material.
Resin has a high water absorption capacity of several tens to several hundred times its own weight,
Water-swellable cross-linked polymerization in the present invention, which is called a water-absorbent resin
It is preferred as a body. Examples of the water-absorbing resin include starch-based resins and cellulosic resins.
Base and synthetic polymer systems.
Is polyacrylic acid type, starch / polyacrylic acid type,
Rivinyl alcohol / polyacrylic acid, polyvinyl alcohol
Alcohol, polyacrylamide, polyoxyethylene
And water-absorbing resins such as epoxy resins. They are
"Superabsorbent polymer" (Fuyoshi Masuda, Kyoritsu Shuppan 198)
(Issued in 7 years). In the present invention, the water-swellable crosslinked polymer is
The water absorbent resin powder described above can be used. these
Is used in concentrated solutions such as sodium sulfate,
Those which are hardly affected by the electrolyte are preferred. Water swellable crosslink
Amount of polymer or water-soluble acrylic polymer to be described later
Is based on 85.0 to 99.5 parts by weight of the inorganic salt composition.
And 0.5 to 15.0 parts by weight, preferably the inorganic
0.5 to 90.0 to 99.5 parts by weight of the salt composition
10.0 parts by weight. Thickening when less than 0.5 parts by weight
Unfavorable due to low effect, exceeding 15.0 parts by weight
This is not preferred because it is too viscous and difficult to handle. As another example of the water-swellable crosslinked polymer,
In the presence of the inorganic salt composition described above, unsaturated carboxylic acid, organic
Unsaturated sulfonic acids and their salts,
At least one monomer selected from amide and a multifunctional monomer
Weight obtained by polymerizing a monomer with a polymerization initiator
Coalescing is available. As unsaturated carboxylic acids, acrylic acid,
Methacrylic acid, hydroxyethyl acrylic acid, itacone
Acids and the like are exemplified. As organic unsaturated sulfonic acids,
2-acrylamido-2-methylpropanesulfonic acid,
p-styrenesulfonic acid, sulfoethyl methacrylate
G, allylsulfonic acid, methallylsulfonic acid, etc.
Is shown. Further, these salts include alkali metal salts.
Or those that are easily soluble in water, such as ammonium salts, are preferred.
No. More preferably a sodium salt can be used
You. Sodium acrylate or sodium methacrylate
Is the most preferred. Unsaturated carboxylic acid, organic
Unsaturated sulfonic acids and their salts with acrylamide
By changing the charge ratio and copolymerizing,
Copolymers having different anionic properties can be obtained. this
The anionic proportion may affect the phase change temperature.
You. For example, the ratio of acrylamide is 50 to 90 mol%
Is preferred. The amount (polymer amount) of these monomers used is
Use the amount corresponding to the amount of the water absorbent resin described above.
Can be. About 1 to 15 weight based on the whole heat storage material composition
%, Preferably 2 to 8% by weight, more preferably 3 to 6 layers
%. If it is less than 1% by weight, the viscosity is low,
Effect of preventing precipitation of sodium sulfate anhydrous
Become. Unnecessarily high concentration exceeding 15% by weight
Then, the heat storage decreases. Polyfunctional monomers are used to crosslink the polymer.
Used for Preferably a water-soluble polyfunctional monomer is used
I have. Specifically, N, N'-methylenebisacrylamido
, N, N'-methylenebismethacrylamide, N,
N'-dimethylenebisacrylamide, N, N'-dimethyl
Tylene bismethacrylamide is exemplified. Preferred
Or N, N'-methylenebisacrylamide or N, N
N′-methylenebismethacrylamide can be used.
Wear. The amount used is 0.005 to 0.5 with respect to 1 mol of the monomer.
In the range of 2 mol, preferably in the range of 0.01 to 0.1 mol%.
It is an enclosure. If the amount is less than 0.005 mol, the crosslinking effect is poor,
If it exceeds 0.2 mol, the effect corresponding to the added amount will not be obtained
Is not preferred. The above monomer and polyfunctional monomer are as follows:
As a result of the polymerization reaction described in
You. Ratio of the water-swellable crosslinked polymer in the heat storage material composition
Is the sum of the amounts of the above monomers and the polyfunctional monomers used.
And 85.0 to 99.5 parts by weight of the inorganic salt composition.
And 0.5 to 15.0 parts by weight, preferably the inorganic salt
0.5 to 1 with respect to 90.0 to 99.5 parts by weight of the composition.
0.0.0 parts by weight, more preferably the inorganic salt composition
2 to 5.5 parts by weight with respect to 5 to 98.0 parts by weight.
You. As the polymerization initiator used in the polymerization,
Acetyl peroxide, lauroyl peroxide and benzoic peroxide
Diacyl peroxides such as il, cumene hydroperoxy
Such as hydroperoxides, di-tert-butyl
Alkyl peroxides such as peroxides,
Ammonium or potassium disulfate, hydrogen peroxide, 2,
Well-known radical weight such as 2-azobisisobutyronitrile
Conventional amounts of coalescence initiator can be used. Above all, redo
Is preferred because the polymerization initiator is active at relatively low temperatures.
Good. Redox weight suitably used in the present invention
Water-soluble initiators are commonly known as initiators.
Things. As an oxidizing agent, ammonium peroxydisulfate
Or potassium, hydrogen peroxide, etc.
Sodium thiosulfate, sodium sulfite, sulfuric acid first
There is iron. The temperature for crosslinking polymerization is sodium sulfate 1
0 or more than the melting point of the hydrate or its eutectic salt, not necessarily
Although not limited, it is usually performed at 20 to 50 ° C. The redox-based polymerization initiator comprises
Mixing oxidizing agent and reducing agent can increase polymerization activity in a relatively short time.
Express. Contact with oxygen in air after polymerization activity has developed
When it is deactivated. Therefore, after mixing both, empty as much as possible
Delivered to containers that polymerize quickly without contact with air.
Need to be done. There are various embodiments for carrying out the method of the present invention.
is there. For example, polymerization is performed in a relatively large vessel,
Heat storage material is divided into containers that constitute the heat storage part of the heating system
There is a method of filling. Preparing a large container for polymerization with nitrogen
Replace with gas, mix each raw material component,
Perform polymerization. In the method of the present invention, the raw material is a crosslinked polymer
Since the monomer is used instead of using
Easy. In addition, polymerization is carried out in a heat storage container such as a heating device.
There is a way. The features of the present invention are particularly advantageous in this method.
Will be demonstrated. In the method of the present invention, the starting material
Since a monomer is used instead of a bridge polymer, etc.
The mixed material is a low viscosity liquid composition. Therefore,
Easily mix materials, even in large and complex containers
Can be injected. By performing polymerization in a container
Heat storage material that is a viscous liquid or jelly-like solid
It can be easily stored in a container having a complicated shape. container
When performing polymerization by filling the mixed material in the
It is not necessary to perform nitrogen replacement in the container. In a container for storing the heat storage material, a liquid set before polymerization is placed.
As a method of injecting the product, for example, as a polymerization initiator
When using a redox initiator, use an oxidizing agent and a reducing agent.
The composition is poured into a container while being continuously mixed in a flow system.
Is desirable. For example, sodium sulfate or its eutectic salt
During injection of the liquid composition of monomers such as water into the container,
A method of separately adding an agent and a reducing agent, and adding an acid to the liquid composition.
Dissolve agent or reducing agent and pour into container
A method of adding the other halfway, dividing the liquid composition,
Dissolve the oxidizing agent on one side and the reducing agent on the other
A method in which both liquids collide and mix in the injection path and are injected into a container
There are laws. Liquid flow path for more efficient mixing
It is also conceivable to put an in-line mixer in the container. In the method of the present invention, the mixed raw materials are placed in a container.
After the injection, the polymerization reaction of monomers etc. proceeds and the viscosity increases
In the meantime, anhydrous sodium sulfate and other additives
Add a thickener in advance to prevent sedimentation in the vessel
It is also preferable to increase the viscosity of the aqueous medium by
Is the law. Known thickeners used for this purpose
Various thickeners are used, for example, fumed silica,
Inorganic substances such as finely divided silica, various clays, polyacrylic acid
Water-soluble polymers such as thorium, water-absorbing resins and the like
You. The amount of the thickener used is about 0.1 to 7% by weight,
Shortened until the polymerization and cross-linking reaction of the monomer etc. proceed and the viscosity increases
Viscosity enough to prevent sedimentation of anhydrous sodium sulfate over time
In an amount that does not lose liquidity.
I just need. Water-soluble acrylic polymer used in the present invention
As, for example, known as an acrylic polymer flocculant
Can be used. Specifically, polyacrylic
Luamide, partially hydrolyzed polyacrylamide, polyac
Sodium acrylate and acrylamide-sodium acrylate
A thorium copolymer and the like can be exemplified. Polyoxyalkylene used in the present invention
As a surfactant having a chain, sodium sulfate 10 water
Anything that has an effect on the crystal form of the salt
There is no particular limitation, and any of them can be used.
Surfactant with Tylene Chain, Polyoxypropylene Chain
Surfactants having the following.
Surfactants having xylene chains are preferred. The present invention
Surfactant having polyoxyethylene chain
As an anion having a polyoxyethylene chain,
Nionic and cationic surfactants are used. The anio
Examples of surfactants include polyoxyethylene alcohol.
Kill ether sulfate, polyoxyethylene alcohol
And the like, phenylphenyl ether sulfate. Examples of the nonionic surfactant include
Lioxyethylene alkyl ether, polyoxyethylene
Alkyl allyl ether, polyoxyethylene sorby
Tan fatty acid ester, polyoxyethylene fatty acid esthetic
And so on. Examples of the cationic surfactant include:
And polyoxyethylene alkylamine. The amount of these surfactants used is the
0.01 to the salt composition of 90.0 to 99.5 parts by weight.
-5.0 parts by weight, preferably 0.05-5.0 parts by weight
And when less than 0.01 parts by weight, the effect of addition is not significant.
If the amount exceeds 5.0 parts by weight, the effect is no longer added even if added.
No improvement is seen. A supercooling inhibitor is added to the composition of the present invention.
be able to. Add a supercooling inhibitor to the mixture before polymerization.
It may be added or may be added after polymerization. However
Then, polymerization is carried out in the container in which the heat storage material composition is finally stored.
Must be added to the mixture before polymerization.
You. Generally, tetraboric acid is used as a supercooling inhibitor.
It is well known that sodium decahydrate is effective.
You. The amount used is about 2-5% by weight of the whole heat storage material,
Add more than saturated solubility in aqueous medium in the operating temperature range
Any amount is sufficient. Sodium tetraborate decahydrate is aqueous
The pH range that exists stably in the medium is neutral to basic
If acidification occurs due to monomers and polymers,
It is desirable to neutralize with alkali. Next, the present invention will be described in more detail by way of examples.
However, the present invention is not limited to these examples.
Absent. Example 1 Anhydrous sodium sulfate 7.291 was placed in a 100 ml beaker.
g, ammonium chloride 4.944 g, sodium tetraborate
0.900 g, polyoxyethylene alkyl phenol
35% sodium ruether sulfate aqueous solution (Kao Corporation)
Product name: Emar NC-35) 0.570 g, water 1
Collect 5.728 g, and heat and shake in a 40 ° C water bath for 30 minutes.
Water-absorbent resin powder (manufactured by Sumitomo Chemical Co., Ltd.
Name: Sumika gel) 0.800 g was added with stirring,
Immediately 33mm diameter, 50mm height screw made of glass
After pouring into a tube, it becomes a non-fluid hydrogel after 3 minutes.
Was. A thermocouple was inserted into this, and the temperature was changed to 22 ° C. and −2 ° C.
Gives a temperature history that repeats the heating and cooling cycle between
Was. Figure 1 (1) shows the coagulation curve at the time of cooling in the 10th cycle.
Show. The solidification curve gives a single plateau, the temperature of
7.6 ° C., in the range of 6-14 ° C. 100
The solidification curve at the cycle was exactly the same. Table 1 shows the results
Are collectively described. In Table 1, as the indication of the melting point,
The starting point of the plateau of the melting curve is the melting start temperature and the ending point
Was shown as the melting end temperature. Examples 2 to 4 and Comparative Examples 1 to 4 In the same manner as in Example 1, compositions having the compositions shown in Table 1 were prepared.
Made. Solidification curve by the same temperature history test as in Example 1.
The temperature of the line was as shown in Table 1. Comparative Example 1
FIG. 1 (2) shows a solidification curve when the temperature of the cycle is lowered. Example 5 Acrylic acid was neutralized with aqueous sodium hydroxide solution to pH 7.5.
Sodium acrylate 10% by weight aqueous solution 1
To 8.000 g, 15.100 g of water is further added, and 30
While stirring at N ° C.
Amide 0.148 g, anhydrous sodium sulfate 15.342
g, 11.558 g of ammonium chloride, sodium tetraborate
1.800 g of sodium octahydrate and polyoxyethylene
Sodium alkyl phenyl ether sulfate 35% aqueous solution
(Manufactured by Kao Corporation, trade name: Emar NC-35) 1.1
4 g was added to obtain a mixture. Sodium sulfate of this mixture
The molar ratio of water (in terms of anhydride) to water is as shown in Table 1.
Was. The mixture is divided into two parts, one of which is
0.060 g of ammonium disulfate
After adding and mixing 0.060 g of pentahydrate,
Each of them flows out of its own channel to form a liquid stream,
While colliding and mixing the flow, a diameter of 33 mm × height of 50 mm
It was poured into a glass screw tube. Put this at 25 ° C
After standing for 1 hour in an atmosphere, observation
The reaction proceeds, and the contents become a uniform jelly-like elastic polymer.
I was A thermocouple was inserted into the obtained polymer,
Temperature cycle between temperature rise and fall between -2 ℃
Gave a history. Fig. 2 shows the coagulation curve at the time of cooling in the 10th cycle.
This is shown in (3). The solidification curve gives a one-step plateau,
Its temperature is 6.3 ° C and is in the range of 6-14 ° C.
Was. The solidification curve at the 100th cycle was exactly the same. Comparative Example 5 In Example 4, the difference was that no surfactant was added.
Outside is exactly the same as in Example 4, except that a glass screw tube
A jelly-like elastic polymer was obtained therein. In the same manner as in Example 4.
The measured solidification curve (10th cycle) is shown in FIG.
You. The coagulation curve gives a plateau of 5.2 ° C., 6-14
It did not fall within the range of ° C. This behavior is the 100th cycle
Was exactly the same. Example 6 Acrylic acid was neutralized with aqueous sodium hydroxide solution to pH 7.5.
30% by weight aqueous solution of sodium acrylate obtained by summing
To 498 g, 12.179 g of water was further added, and acrylic
1.354 g of amide, N, N'-methylenebisacryl
Amide 0.019 g, polyoxyethylene alkylphen
35% aqueous solution of sodium nitryl sulfate (Kao Corporation)
(Trade name: EMAL NC-35)
The mixture was stirred and dissolved at room temperature for 10 minutes. Then, 6.014 g of ammonium chloride, salt
0.821 g of sodium chloride was added, and the mixture was placed in a 35 ° C water bath for 10 minutes.
After heating and stirring, anhydrous sodium sulfate (7.981 g) was added.
The mixture was further heated and stirred for 30 minutes. Put this in a 20 ° C water bath
Transfer and add 2.490 g of sodium tetraborate
After stirring for 2 hours, transfer to a 40 ° C water bath and stir for 10 minutes
did. Next, water-absorbent resin powder (Sumitomo Chemical Industries, Ltd.,
(Trade name: Sumika gel) 0.300 g was added and stirred for 2 minutes
After stirring, 0.030 g of potassium peroxydisulfate was added.
Dissolve 0.030 g of sodium sulfate in 2.027 g of water
The solution was added to the above mixture, and as a result, after 30 seconds,
It became a lee-like elastic body. A thermocouple was inserted into this, and the temperature was set at 22 ° C. and −2 ° C.
Gives a temperature history that repeats the heating and cooling cycle between
Was. Coagulation curve at 20th cycle gives one step plateau
The temperature (freezing point) is 7.6 ° C,
Was within the range. No solidification curve at 100th cycle
It was similar. Example 7 In Example 6, 30% by weight of sodium acrylate in water
3.411 g of the solution, 0.775 g of acrylamide,
Same as Example 6 except that 10.802 g of water was added.
By operation, a jelly-like elastic body was obtained. The freezing point is 7.6 ° C
there were. Example 8 In Example 6, 30% by weight of sodium acrylate in water
1.800 g of acrylamide, water 1
The same operation as in Example 6 except that 3.145 g was added.
Thus, a jelly-like elastic body was obtained. The freezing point is 6.0 ° C
Was. Example 9 Water-absorbing resin powder (manufactured by Sumitomo Chemical Co., Ltd., trade name: Sumi
Kagel) until 0.300 g is added and stirred for 2 minutes
The same operation as in Example 6 is performed to obtain a mixture. This mixture
Divide the product into two parts and add potassium peroxydisulfate to one
Solution dissolved in water, and sodium sulfite dissolved in water
After adding and mixing the aqueous solutions,
Out of the channel into a liquid stream, and collide and mix the two liquid streams.
, 33mm diameter x 50mm height glass screw tube
Inject into When this is left standing in an atmosphere of 25 ° C.
The crosslinking reaction proceeds, and the content becomes a uniform jelly-like elastic body.
The obtained jelly-like elastic body has the same characteristics as in Example 6.
You. Example 10 In a 50 ml glass screw tube, 15.193 g of water and
Lioxyethylene alkylphenol ether sulfate nato
35% aqueous solution of Li (manufactured by Kao Corporation, trade name: Emar)
NC-35) 0.577 g, ammonium chloride 6.01
3g and 0.822g of sodium chloride were collected and bathed at 35 ° C.
After heating and stirring for 10 minutes, anhydrous sodium sulfate 7.9
82 g was added and the mixture was further heated and stirred for 30 minutes. This is 20
Transfer to water bath and add sodium tetraborate 2.490 g
The mixture was stirred for 2 hours while keeping the system open. Then, the partial hydrolysis
Liacrylamide (Sumitomo Chemical Industries, Ltd., polymer aggregation)
Agent, trade name: Sumifloc FN-15H) 1.802 g
Was added, and the mixture was stirred with a spatula until it became jelly-like.
Insert a thermocouple into this and raise and lower the temperature between 22 ° C and -2 ° C.
A temperature history that repeats the temperature cycle is given. 20 cycles
The solidification curve gives a one-step plateau, and its temperature is
7.6 ° C., in the range of 6-14 ° C. 100
The solidification curve at the cycle was exactly the same. Comparative Example 6 In Example 10, no surfactant was added.
Except for this point, the glass screw was made in exactly the same manner as in Example 10.
-A jelly-like elastic polymer was obtained in the tube. Same as Example 10
Temperature history test gives a one-step plateau
The temperature is 5.8 ° C, which falls within the range of 6 to 14 ° C.
I didn't. The 100th cycle solidification curve is exactly the same
there were. In Table 1, abbreviations represent the following. 1. Composition of Inorganic Salt and Polymer Inorganic Salt: Compounding molar ratio (sodium sulfate decahydrate 1 mol
Polymer: acrylamide / sodium acrylate (mol
Ratio) A1: 1.8 mol of ammonium chloride, 7.0 mol of water acrylamide / sodium acrylate = 0/100 A2: 2.0 mol of ammonium chloride, 6.0 mol of water acrylamide / sodium acrylate = 0/100 B1: 2.0 mol of ammonium chloride, chloride
Sodium 0.25 mol, water 5.0 mol acrylamide / sodium acrylate = 80/20 B2: ammonium chloride 2.0 mol, sodium chloride
0.25 mol, water 5.0 mol acrylamide / sodium acrylate = 50/50 B3: 2.0 mol of ammonium chloride, sodium chloride
0.25 mol, water 5.0 mol acrylamide / sodium acrylate = 100/0 B4: 2.0 mol of ammonium chloride, sodium chloride
0.25 mol, water 5.0 mol acrylamide / sodium acrylate = 95/5 (parts
(Using polyacrylamide partially hydrolyzed) Type and amount of surfactant C: polyoxyethylene nonyl phenyl ether sulfate
Thorium (manufactured by Kao Corporation, trade name: Emar NC-3)
5) 1% by weight D: polyoxyethylene alkylamine (Kao Corporation)
(Product name: Amit 308) 1% by weight E: polyoxyethylene monooleate (Kao Corporation)
Manufactured and trade name: Emanone 4110) 1% by weight F: polyoxyethylene sorbitan monola
Urate (made by Kao Corporation, trade name: Leo Doll Super
TW-L120) 1% by weight G: sodium dodecylbenzenesulfonate (Kao
Product name: Neoperex F-25) 1 weight
% H: sorbitan sesquioleate (manufactured by Kao Corporation, product
Name: Reodol AO-15) 1% by weight I: Special carboxylic acid type (manufactured by Kao Corporation, Trade name: Latem
ASK) 1% by weight The specific inorganic salt composition of the present invention, water swelling property
Crosslinked polymer or water-soluble acrylic polymer, and surfactant
The heat storage material composition composed of a surfactant has a temperature suitable for air conditioning and cooling.
It has a melting point and freezing point within the range, and the melting point and freezing point
Is appropriate, and melting in long-term use
・ Stable enough to withstand repeated solidification.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows a solidification curve in a temperature history test of repeated melting and solidification of Example 1 and Comparative Example 1. FIG. 2 shows a solidification curve in a temperature history test of repeated melting and solidification of Example 5 and Comparative Example 5. [Explanation of Codes] Example 1 2. Comparative Example 1 3. Example 5 4. Comparative Example 5

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-61-111389 (JP, A) JP-A-59-60197 (JP, A) JP-A-55-66984 (JP, A) JP-A-58-58 221395 (JP, A) JP-A-5-25467 (JP, A) JP-A-62-25188 (JP, A) JP-A-58-132075 (JP, A) JP-A-57-47339 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09K 5/06 F28D 20/00

Claims (1)

(57) [Claims] (1) 1.5 to 2.5 mol of ammonium chloride and 1 mol of water per mol of sodium sulfate (in terms of anhydride)
85.0-99.5 parts by weight of an inorganic salt composition containing 0 to 27 mol, (2) 0.5 to partially hydrolyzed polyacrylamide
15.0 parts by weight, (3) polyoxyethylene alkyl ester
Tersulfate and polyoxyethylene alkyl
Less selected from phenyl ether sulfate
A heat storage material composition comprising 0.01 to 5.0 parts by weight of one kind of a surfactant as a main component.