JPH1095970A - Heat insulating agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat insulating agent composition as a dry powdery material, showing an excellent handling property, also exhibiting excellent low cost property and safety, and useful for keeping a fresh food cool, etc., by combining a specific porous silica, a porous clay mineral and a coolant water. SOLUTION: This heat insulating agent composition has a particle shape of a granular powdery material, and contains (C) 40-65wt.% coolant water in a form of free water in a mixed powdery material system obtained by uniformly mixing (A) a porous silica powder [e.g.; having <=0.3g/ml bulk density (Z1 ) and >=180ml/100g oil absorbing amount (Z2 )] having 1-20μm mean particle diameter with (B) a porous clay mineral powder [e.g.; having <=0.5/ml (Z1 ) and >=150ml/100g (Z2 )] having 5-30μm (d) in a ratio of 100 pts.wt. component (A) to 0-100 pt.wt. component (B) based on 110 deg.C dried material, and having >=60% accumulated pore volume having 100-10,000Å range pore radius per total pore volume.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic refrigerating composition used for various types of preservation and preservation of cold, and more particularly, to a free-flowing powder which is freezing and freezing when cooled. The present invention relates to a refrigerating composition which is a granule.

[0002]

2. Description of the Related Art In recent years, a water-retaining material in which a water-containing viscous material of a water-absorbing resin and a fine inorganic powder such as silica is loaded in a plastic bag made of polyethylene or the like, or a viscous material content of the refrigerating material has been developed. Hospitals, such as plastic bags made of colloidal silica sol and water-soluble organic polymer
It is widely used in individuals' homes for ice sacs and ice pillows, and for cooling and preserving fruits, fresh foods, soft drinks and the like in ice boxes for recreational use, for example.

[0003] All of these cold insulators are once cooled or frozen in a freezer, and the bag does not harden firmly in a temperature range of about 5 ° C where a cold insulator is expected to be used substantially. It has flexibility to bend, and is designed to be used, for example, in close contact with an affected part, or to be used in close contact with the shape of a container of fresh food or soft drink, and to be efficiently kept cool.

For example, superabsorbent resins and aerosil, silica gel, zeolite, diatomaceous earth, talc, kaolin,
Water-containing compositions with inorganic powders such as bentonite and activated clay (Japanese Patent Laid-Open No. 4-81492);
Gel comprising a polyvalent metal salt of boric acid and boric acid and a porous filler (Japanese Patent Application Laid-Open No. 4-222892), contains sepiolite as a gelling agent in carrageenan, and contains water-soluble polyvalent alcohol and the like. Aqueous gel-like low-temperature flexible cooling agent (Japanese Patent Laid-Open No. 3-6286), a viscous composition obtained by adding a water-soluble cellulose ether to a colloidal silica sol (Japanese Patent Laid-Open No. 6-17037), density 0 .925 g /
ml of an ethylene-α-olefin copolymer base material impregnated with an oily substance (JP-A-6-192647)
Representative cold storage agents have been proposed.

[0005]

However, all of the cooling agents proposed in the above-mentioned publications have an organic component as a main material, and in the unlikely event that the bag of the product is damaged during use, the cooling agent for the contents is not used. Is still lacking in safety when scattered around, and many of the cooling agent compositions are water-containing organic viscous substances, and if left for a long time, they will be decomposed by the action of bacteria, etc. There is a problem such as the generation of substances, and a material that is cheaper in cost is required.

[0006] Furthermore, there is a demand for a cooling agent product which still lacks flexibility in the conventional products, and has a feeling as a pillow containing rice hulls as a pillow for heat cooling. Not provided.

[0007] Accordingly, an object of the present invention is to provide an inorganic refrigerating agent which is inexpensive and safer to handle than conventional organic refrigerating agents, and has a smooth refrigerating agent composition. An object of the present invention is to provide a cooling agent composition which is granular and has excellent handleability.

[0008]

According to the present invention, there is provided a porous silica having an average particle diameter of 5 to 30 μm per 100 parts by weight of a porous silica powder having an average particle diameter of 1 to 20 μm and dried at 110 ° C. A system in which 0 to 100 parts by weight of a clay mineral powder is uniformly mixed on a dry basis at 110 ° C., wherein the total pore volume of the mixed powder system is 1.5 ml / g or more, Per pore radius 100 to 1000
Provided is a refrigerating agent composition characterized in that the particle shape is a powder having a pore volume of 0 Å or more in a range of 60% or more and free water contained in the system of 40 to 65% by weight. You.

That is, more specifically, the refrigerant composition according to the present invention is a refrigerant composition in which all components composed of a combination of porous silica, a porous clay mineral and a coolant water are inorganic, The bulk density of silica is 0.3 g / ml or less and the oil absorption is 180 ml / 100 g or more, while the bulk density of the porous clay mineral is 0.5 g / ml or more and the oil absorption is 150 ml / 100 g or less. Refrigerant water is used as free water in a homogeneous mixture system of both powder components with certain characteristics.
It is a powder containing 0 to 65% by weight, and all of the components are made of an inorganic material with a smooth appearance.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, a product having a cooling function which is the object of the present invention has been
The shape of the plastic bag is flexibly bent, and the cooling agent composition of the bag must not be frozen and solidified when used. Therefore, also in the present invention, the present refrigerant agent is characterized by the fact that the present refrigerant agent composition does not become a solid freezing continuum due to the moisture contained as free water in the refrigerant component of the present refrigerant agent composition. Is what it is.

As described above, the refrigerant composition according to the present invention has an average particle size of 1 to 20 μm on a dry matter basis at 110 ° C.
per 100 parts by weight of porous silica powder having a mean particle diameter of 5 to 30 μm, and water as a refrigerant is mixed in a system obtained by uniformly mixing 0 to 100 parts by weight on a dry matter basis at 110 ° C. The particle shape is 40 to 65% by weight in the form of free water, and the composition is characterized in that the composition has an average particle size of 10 to 30 μm. It is.

[0012] Further, a further feature of the cold-retaining agent composition is that, unlike the conventional cold-retaining agent in which the main ingredient is organic, all components are inorganic and the inorganic material of the base material sufficiently contains water. It is a powdery and granular material that has a rough appearance in a state in which it is a solid body and that sufficiently contains water as a refrigerant. Therefore, when processing into bag-shaped products using this cold storage agent, for example, a polyethylene bag can be easily filled with the powdered and granular form of this agent, which makes handling easier than conventional viscous fluid cooling agents. It has excellent properties.

In order for the above-mentioned powdery / granular composition to exhibit sufficient performance to be put to practical use as a refrigerating agent, which is the object of the present invention, water as a refrigerant should be 40 to 65% as free water.
It must be in the range of weight percent. In the present invention, when the water content is 40% or less, the cooling time based on JIS-S-3105 described in Examples described below is 3 hours or less, which is not practical. Even below, it is not yet sufficiently satisfied in practice.
On the other hand, if the content is 65% or more, water is likely to be generated in the above-mentioned granular composition system, and the cooling agent composition after cooling becomes a firm solid as a whole, or the contents of the bag are subjected to omni-distribution. It does not satisfy the purpose of the invention.

The upper limit of the water content of the free water is as follows.
The system is filled with water as a refrigerant sufficiently and shakes vigorously when the system loaded in the bag as a loose powder or granule is not used, or the bag is compressed, or changes such as repeated bending are given. As a result, the free water contained in the pores is liberated as syneresis water, and the whole becomes net-like mass (paste-like) or drotted slurry-like. Therefore, when such a system is cooled in a freezer, the cooling agent composition becomes a uniform hard frozen state by syneresis water and is not the cooling agent targeted by the present invention.

In the present invention, as described above, the total pore volume of a system obtained by uniformly mixing 0 to 100 parts by weight of a porous clay mineral powder per 100 parts by weight of a porous silica powder is a refrigerant. It is at least 1.5 ml / g or more, preferably 1.8 ml / g because it contains a lot of water.
It is important that the first condition is at least 2 ml / g.

In addition, the pore volume is such that the cumulative pore volume having a pore radius in the range of 100 to 10000 angstrons per total pore volume is 60% or more, preferably 70% or more, more preferably 80% or more. This is important as the second condition. In the present invention, the above-mentioned pore volume is called an effective pore volume, as described later.

That is, in the experiment NO. 1 to 5
From the fact that pores having a pore radius of 100 Å or less are difficult to absorb water, a pore volume in this range is not effective for the present invention, and pores having a pore radius of 10,000 Å or more are water It is assumed that it is not effective for the present invention because it is easy to absorb but it is easy to remove the powder, and because the refrigerant of the present invention forms powder and granules, and the product of the bag is flexible. Because it is done.

Therefore, most of the pores of the refrigerant powder of the present invention are composed of mesopores having a pore radius of 100 Å or more as described above and macropores having a pore radius of 10,000 Å or less. The feature is that, for that purpose, the refrigerant powder of the present invention may be composed of only porous silica as long as the effective pore volume described above is sufficient, but many of the conventional porous silica In general, even if the total pore volume is large, most of the pores occupied by the pore volume are generally formed by mesopores or micropores of 1000 Å or less. Therefore, only the conventional porous silica has a small effective pore volume containing a large amount of free water as a refrigerant which is not easily released.

Therefore, in the present invention, the porous clay mineral powder based on the dry matter at 110 ° C. is composed of 10 to 100 parts by weight, preferably 40 to 100 parts by weight, based on 100 parts by weight of the silica powder based on the dry matter at 110 ° C. In addition, by using different binary compositions having different physical properties as in the present invention, both aggregating forces work uniformly when both powders are agitated and mixed, so that powders having better handleability are formed.

As a result, as is apparent from the examples described later, the powder thus formed tends to increase the mesopores or macropores more synergistically than the silica alone, and The ratio of the effective pore volume to the pore volume is 7
It is assumed that the water content increases to 0% or more, preferably 80% or more, so that the free water contained can be more stably occluded to form powders that are difficult to be separated, and these are in good agreement with the facts of the examples. I have.

In particular, in the present invention, the length of the cooling time evaluated by the above-mentioned test method becomes longer in proportion to the amount of free water as a refrigerant. The fact that the cold preservation time is made extremely long by making the powder of a binary composition composed of a combination of porous clay minerals is an unexpected result even for the present inventor, and this fact is This is a very important feature of the invention.

Although the details are unknown, the fact that the bulk density of one of the porous silica powders is 0.3 g / ml, even if the specific surface area is substantially the same, will be explained from the fact of the examples described later.
And the oil absorption is 180 ml / 100 g or more, and the bulk density of the other porous clay mineral powder is 0.5 g / m
When the combination of the two powders is not less than 1 and the oil absorption is 150 ml / 100 g or less, the combination of the binary compositions having different powder properties from each other makes it possible to obtain the inside of the powdery particles as a mixed powder system. Alternatively, it is assumed that air that blocks heat is uniformly contained in pores or gaps formed between the particles, and the air layer acts as a heat insulating layer for heat.

Such a fact is, as already mentioned, 65%.
This is in good agreement with the fact that the air layer acts to prevent particles from adhering to form smooth powder particles while containing water.

As a result, according to the present invention, the product of the bag body is flexible, for example, because it is a granular material, and when used as a pillow for heat cooling, a feeling of pressure is applied to the neck like a pillow containing rice husks. It seems that a cold pack product having a soft touch that was not felt could be provided.

(Cold Keeping Composition and Method for Producing the Same) The porous silica used in the present invention has a BET ratio evaluation area of 140 to 6%.
Since it is more preferably used as the porosity is larger, the specific surface area is preferably larger. The average pore diameter is 120 to 220 Å, and the oil absorption may be 150 ml / 100 g or more, preferably 200 to 300 ml / 100 g. There is no particular problem if the particle diameter is in the range of 1 to 30 mμ, preferably 5 to 20 mμ. Further, the bulk density is preferably 0.3 g / ml or less, more preferably 0.2 g / ml or less.

What is particularly important in the present invention is that it has a large pore volume and a pore size suitable for absorbing water serving as a refrigerant. Therefore, in the present invention, the total pore volume is in the range of 1.8 to 3 ml / g, preferably in the range of 2 to 2.5 ml / g, and the pore radius is 100 to 400 ml / g. 1000
Porous silica having a pore volume of 0 Å or more in the range of 60% or more, preferably 70% or more, particularly preferably 80% or more is suitably used.

The other porous clay mineral has a BET specific surface area of 70 to 350 m 2 / g, preferably 100 m 2 / g.
2 / g or more and oil absorption of 30 to 150 ml / 10
0 g and a pore volume of 0.15 to 0.9 ml /
g, preferably 0.3 to 0.7 ml / g, particularly preferably 0.4 to 0.6 ml / g.

In the present invention, a layered or chained clay mineral porous body having a pore volume of the above-mentioned size as compared with the silica porous body but having a structurally different structure is used. By combining them, the cooling time can be remarkably increased, and an unexpected synergistic effect is exhibited (for example, S- of silica alone in Experiment No. 1-2).
No. 2 and experiment NO. 4-2 S-2 / C-2 system).

Further, the bulk density is 0.5 g / ml or more,
It is preferably in the range of 0.6 to 0.8 g / ml for the present invention. In particular, even if a material having a bulk density of 0.5 g / ml or less is combined with the above-mentioned porous silica, a powdery / cooling agent composition having a binary composition excellent in handling properties cannot be obtained.

As the porous clay mineral, a two-dimensional layered crystal structure such as montmorillonite, bentonite, and acid clay is used as it is. In particular, activated clay which is an acid-treated derivative of acid clay is preferably used. Is done. The activated clay has a specific surface area of 400 obtained by eluting a part of the iron, magnesium and aluminum constituting the skeleton contained between the layers of the acid clay by the acid treatment of the acid clay.
A highly active clay mineral derivative of acidic clay having a m2 / g or less, which has been widely used as a refining agent for oils and fats.

A magnesium silicate clay mineral, a formite-based chain clay mineral having a three-dimensional chain crystal structure, is also preferably used. These formite-based chain clay minerals have a chain structure and voids formed in the gaps of the converging body having a BET specific surface area of 60 to 400 m2 / g and a converging body structure. Therefore, it is a porous chain-like clay mineral having an adsorption action.

Among the above-mentioned formicite-based magnesium silicate clay minerals, fibrous clay minerals (chain clay minerals) such as sepiolite, palygorskite and attapulgite are preferably used. In the present invention, among the chain clay minerals of the above-mentioned 3-octahedral magnesium silicate clay minerals, they are produced in various parts of the world and are relatively easily available, and their shapes are fibrous as viewed by silent observation. Alternatively, sepiolite, which is a convergent body observed by microscopic observation, is preferably used.

Hereinafter, a method for producing a cooling agent composition having a typical composition of the present invention using the above-mentioned powder raw materials will be described. A commercially available porous silica powder satisfying the above requirements (specific surface area: 145 m2 / g, pore volume: 2.4 ml /
g, bulk density 0.27 g / ml, water content 7.5%) and commercially available sepiolite powder (specific surface area 175 m 2 / g, pore volume 0.8 ml / g, bulk density 0.58 g / ml, water content 1
0.8%) in a super mixer at a weight ratio of 1: 1 and pre-mixed for about 1 minute, and then water was stirred under stirring such that the final water content was 60%. It is added and stirred under the condition of about 500 to 1200 rpm to prepare a refrigerating agent composition of the present invention composed of a powder having an average particle size of 17 μm and a smooth appearance.

The sepiolite used as the raw material of the present invention may be pulverized in advance with a ball mill, a hammer mixer, or a kneaded pulverizer using a Henschel mixer, a super mixer, a mortar, or the like, if necessary. It is preferable to perform primary pulverization treatment by impact pulverization with an atomizer, a jet mill or the like, and to partially open or loosen the chain structure as a converging body and the laminar structure as scaly before use.

As long as the water content of the refrigerant composition is not reduced, as described above, if the adsorptivity of sepiolite is utilized, at least one of antibacterial components such as silver, zinc, copper, and iron is used. Sepiolite impregnated or ion-exchanged may be used as a raw material. Also, in activated clay, if its cation exchangeability (CEC) is used,
Similarly to sepiolite, activated clay obtained by depositing the above ionic species is also used as a raw material.

(Uses) The powder-shaped refrigerating agent composition according to the present invention is used as a product in the form of an ice bag and ice pillow in hospitals and private homes in the form of a product which is hermetically packed in a flexible resin bag as described below. Also, it can be widely used for cooling and preserving fresh foods, soft drinks and the like in ice boxes for recreational use.

These resins include, for example, polyolefins, ethylene / vinyl acetate copolymers, ethylene / vinyl alcohol copolymers, ethylene / vinyl compound copolymers such as ethylene / vinyl chloride copolymers, polystyrene, acrylonitrile / Styrene copolymer, ABS, α
Styrene resins such as methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride / vinylidene chloride copolymer, polyvinyl compounds such as polymethyl acrylate, polymethyl methacrylate, nylon 6, nylon 6 -6, nylon 6-10, nylon 1
1, polyamides such as nylon 12, and resins such as polyethylene terephthalate and polybutylene terephthalate.

The present invention will be described in detail with the following examples. (Various measuring methods used in the present invention) Apparent density Measured according to JIS K-6220.6.8. 2. Oil absorption The oil absorption was measured in accordance with JIS K-5101.21. 3. Specific surface area and pore volume Sorptomatic Seri manufactured by Carlo Elba
Using es 1800, the specific surface area and the pore volume by the BET method were measured. Using a mercury intrusion porosimeter (Autopore 9220, manufactured by Micromeritics Co., Ltd.), the pore size of 18 to 43500 angstron was measured to determine the pore volume. In addition, the total pore volume refers to the total cumulative pore volume in the range of the pore diameter of 18 to 43500 Å. 4. Effective pore volume Pore diameter occupying 100 to 10,000 per total pore volume
The cumulative pore volume (ml / g) in the Angstron range is defined as the effective pore volume and is expressed as a percentage. 5. Particle size 50 μm aperture tube by Coulter Counter (TA-II type manufactured by Coulter Electronics)
m. 6. Cooling test In accordance with JIS-S-3105 Cooling test method for portable cooler, put the powder sample of the cooler in a polyethylene bag, put it in a freezer for 24 hours and cool it down, then cool it to 23 ~ 27 ℃ Take out in an atmosphere with a relative humidity of 65%, place a nylon fishing line in a frame with legs 10 cm high from the floor, place a sample bag flat on a net with an interval of about 10 mm in length and width, and immediately place it in the center. Was measured every 30 minutes with a digital surface thermometer (manufactured by Adachi Keiki, HFT-40 type), and the time until the surface temperature reached 10 ° C. was defined as the cooling time. 7. Smoothness (flexibility) of the powder of the cooling agent Filling the powder of the cooling agent composition into a 50 ml beaker, gently tapping the bottom of the beaker against the table, leveling the filling surface, and then freezing the refrigerator After putting in the room all day and night, take out and place 200g of weight (weight) on the filling surface, sink depth of the weight (m
m) is measured with a vernier caliper, and the smoothness (flexibility) of the present agent is numerically evaluated from the numerical value of the depth as follows. [Depth] (mm) [Evaluation of granular material] 0-0.1 Consolidation 22- Rough powder (poor handling) 0.15-20 Fairly good granular material 0.5-10 Good In the present invention, the depth is 0.15 to 20 m.
Those in the range of m are evaluated as a powder-shaped refrigerating agent.

[0039]

【Example】

(Example 1) A powdery particulate refrigerating composition according to the present invention containing 40 to 70% by weight as free water in a homogeneous mixture system comprising a combination of a porous silica powder and a porous clay mineral powder is described below. explain. (Porous silica powder) Sample S-1; (Specific surface area: 150 m2 / g, total pore volume: 2.13 g / ml, bulk density: 0.176 g / ml,
Oil absorption: 202 ml / 100 g, average particle size: 14.14
μm, water content: 10%) Sample S-2; (specific surface area: 145 m 2 / g, total pore volume: 2.29 g / ml, bulk density: 0.266 g / ml,
Oil absorption: 200 ml / 100 g, average particle size: 18.46
μm, water content: 7.6%) Sample S-3; (specific surface area: 400 m 2 / g, total pore volume: 2.90 g / ml, bulk density: 0.292 g / ml,
Oil absorption: 240 ml / 100 g, average particle size: 10 μm,
(Moisture content: 7.4%) Sample S-4; (specific surface area: 296 m2 / g, total pore volume: 2.5 g / ml, bulk density: 0.289 g / ml, oil absorption: 180 ml / 100 g, average particle size) Diameter: 8.5 μm,
(Water content: 7.7%) (porous clay mineral powder) Sample C-1; (specific surface area: 166 m2 / g, total pore volume: 0.75 g / ml, bulk density: 0.58 g / ml, oil absorption) : 75 ml / 100 g, average particle size: 11.8 µm,
(Moisture content: 10.8%) Sepiolite powder. Sample C-2; (Specific surface area: 280 m2 / g, total pore volume: 0.45 g / ml, bulk density: 0.61 g / ml, oil absorption: 40 ml / 100 g, average particle size: 11.8 μm,
(Water content: 9.7%) Activated clay powder. Sample C-3; (Specific surface area: 80 m2 / g, total pore volume:
0.45 g / ml, bulk density: 0.71 g / ml, oil absorption: 30 ml / 100 g, average particle size: 8.9 μm, water content: 14%)) ... Acid clay powder.

In this embodiment, using these two powders, Experiment No. 1 to NO. The powder described in No. 5 was placed in a supermixer having a capacity of 50 L, uniformly stirred and mixed, and then a predetermined amount of water was added thereto with stirring to prepare a powdery / cooling agent composition according to the present invention. The water content and free water of both powders are values of a dried product at 110 ° C. for 2 hours. In Tables 1 to 4 below, the specific surface area, oil absorption, total pore volume, and effective pore volume are physical properties of the powder system before adding water as free water.

1. Experiment NO. 1 (single system of S-1 to S-4) (Table 1) Experiment No. 1-1 1-2 1-3 1-4 Silica species S-1 S-2 S-3 S-4 Weight ratio 100 / 0 100/0 100/0 100/0 Specific surface area 150 145 400 296 (m2 / g) Oil absorption 205 200 240 188 (ml / 100g) Total pore volume 2.13 2.29 2.8 2.48 (ml / g) Effective pore Volume 1.81 1.75 1.68 1.51 (ml / g) Bulk density 0.34 0.46 0.5 0.57 0.63 0.49 0.5 0.49 0.55 (g / ml) Angle of repose 44 45 45 46 50 51.1 48.9 Free water (%) 50 55 60 50 55 60 50 55 60 60 Cooling time (hr) 3.1 3.8 5.1 2.36 2.8 3.2 2 3 4.3 4.0 Flexibility (mm) 21 16 11 17 15 8.4 70 28 20 3.96

[0042] 2. Experiment NO. 2 (combination of S-1 and C-1) (Table 2) Experiment No. 2-1 2-2 2-3 2-4 S-1 / C-1 50/50 70/30 80/20 90 / 10 (weight ratio) Specific surface area 160 154 153 153 (m2 / g) Oil absorption 140 158 170 186 (ml / 100g) Total pore volume 1.86 2.23 2.22 2.21 (ml / g) Effective pore volume 1.68 1.75 1.72 1.76 (ml / g) Bulk density 0.57 0.63 0.46 0.53 0.42 0.5 0.37 0.44 0.51 (g / ml) Angle of repose (degree) 46.8 48.8 Free water (%) 50 55 50 55 50 55 50 55 60 Cooling time (hr) 3.95 5.45 4.4 5.2 4.3 5.4 3.6 4.8 5.2 Flexibility (mm) 2.35 0.86 6.26 4.54 9 6.5 10 9.8 9.9

[0043] 3. Experiment NO. 3 (combination of S-2 and C-1) (Table 3) Experiment No. 3-1 3-2 3-3 3-4 S-2 / C-1 50/50 60/40 70/30 80 / 20 (weight ratio) Specific surface area 158 151 (m2 / g) Oil absorption 125 150 (ml / 100g) Total pore volume 1.62 1.83 2.0 2.16 (ml / g) Effective pore volume 1.25 1.41 1.55 1.65 (ml / g) Bulk Density 0.67 0.7 0.64 0.6 0.67 0.67 0.58 0.65 (g / ml) Angle of repose 53.6 47.9 49.3 53.6 Free water (%) 55 57 55 60 50 57 60 50 55 Cooling time (hr) 4.1 4.3 4.0 4.3 3.5 4.4 4.6 3.6 3.9 Flexibility (mm) 0.3 0.23 1.7 0.2 8.1 1.48 0.16 13 6.2

4. Experiment NO. 4 (combination of S-2 and C-1) (Table 4) Experiment No. 4-1 4-2 S-2 / C-2 50/50 70/30 (weight ratio) Specific surface area 213 186 (m2 / g) Oil absorption 120 152 (ml / 100g) Total pore volume 1.65 1.76 (ml / g) Effective pore volume 1.38 1.48 (ml / g) Bulk density 0.67 0.64 0.71 (g / ml) Angle of repose 50.8 48 48.4 Free water (%) 50 55 55 60 Cooling time (hr) 5.0 5.4 5.2 6.02 Flexibility (mm) 6.3 1.7 6.3 1.7

5. Experiment NO. 5 (combination of S-2 and C-3) (Table 5) Experiment No. 5-1 5-2 S-2 / C-3 50/50 70/30 (weight ratio) Specific surface area 113 126 (m2 / g) Oil absorption 115 150 (ml / 100g) Total pore volume 1.52 1.69 (ml / g) Effective pore volume 1.16 1.32 (ml / g) Bulk density 0.68 0.60 0.63 (g / ml) Angle of repose 50.2 44.6 49.3 Free water (%) 50 55 55 60 Cooling time (hr) 4.3 4.76 4.1 4.97 Flexibility (mm) In addition, from the above results, a cooling agent composition having a cooling time of 3 hours or less described in Tables 1 to 5 is used in the present invention. This is a comparative example.
Also

6. Experiment NO. 6 In the following, a cooling test was performed on various comparative examples (H-1 to H-5) in the same manner as in the examples, and the results are shown in parentheses (cooling time and the like). H-1: Free water 40% of sepiolite powder of sample C-1
Granules (consolidation, 3.4 hours). H-2: Granules (consolidated, 1%) of 37% free water at a weight ratio of sample C-3 acid clay to sample C-1 sepiolite of 1/1.
time). H-3: 51% powder (consolidated, 1.1 hours) using seawater of sample S-4 powder as free water. H-4: weight ratio of sample S-4 to sample C-3 acid clay 1
/ 1, free water 53%, total pore volume 1.45 g / ml,
Powder having an effective pore volume of 0.95 g / ml (consolidation, 4 hours). H-5: 54% of free water (5% aqueous solution of calcium chloride) at a weight ratio of 1/1 of sample S-4 to acid clay of sample C-3
(Consolidation, 2 hours). H-6: The same granules (consolidation, 0.7%) as H-5 except that the free water was changed to a 10% aqueous calcium chloride solution in H-5.
time). From Experiments H-4 to H-6, it is understood that it is better that the water used as the refrigerant in the present invention does not contain salts or the like that lower the freezing point (from the heat of melting of ice). ). H-7: Powder and granules of 53% free water (consolidation, 2 hours) at a weight ratio of sample S-4 to sample C-1 sepiolite of 1 / 1.5. H-8: Powder and granules of 30% free water (consolidation, 2 hours) at a weight ratio of 1/1 of the flattery sand having a total pore volume of 0.3 g / ml to the sample C-1 sepiolite.

[0047]

According to the present invention, a porous silica powder and a powder of a porous clay mineral represented by acidic clay, activated clay and sepiolite are used in place of the conventional organic viscous fluid cooling agent composition. By adding 40 to 70% by weight of free water as a cooling medium in a homogeneous mixture with the body, it was possible to provide a completely inorganic refrigerating composition, which was a powder having a smooth appearance of particles. In addition, the plastic bag insulation material filled with the above-mentioned powder and granules is not extremely solidified even when cooled in a freezer, so that it is extremely excellent in flexibility, so that the ice bag for heat-cooling the sick person, for ice pillows, for example, Cooling and preservation can be efficiently performed as a cold preservation material for preserving and preserving fresh foods, soft drinks and the like in the ice box for recreational use.

Claims (7)

[Claims] 2. The method according to claim 1, wherein the average particle size is 1 to 20 μm.
A porous clay mineral powder having an average particle diameter of 5 to 30 μm and a dry clay standard of 110 ° C. is uniformly mixed in a range of 0 to 100 parts by weight per 100 parts by weight of porous silica powder based on 0 ° C. Wherein the total pore volume of the mixed powder system is 1.5 ml / g or more, and the cumulative pore volume (effective pore volume) having a pore radius in the range of 100 to 10000 angstrons per total pore volume. A refrigerating composition, characterized in that the particle shape is 60% or more, and 40 to 65% by weight of free water is contained in the mixed powder system as powder. 2. The bulk density (apparent specific gravity) of the above-mentioned powdery granules is 0.4 to 0.8 g / ml, and the average particle diameter is 10
2. The composition according to claim 1, wherein the composition is a powder having a repose angle of from 40 to 55 [deg.] And a temperature of not more than zero degree Celsius and does not freeze and coagulate with each other. 3. The porous silica powder has a BET specific surface area of 140 to 600 m 2 / g, a bulk density of 0.3 g / ml or less, and an oil absorption of 180 ml / 100 g.
The refrigerating composition according to claim 1 or 2, which is the above. 4. The porous silica powder has an average pore diameter of 1
4. A refrigerating composition according to any one of claims 1 to 3, wherein the composition is in the range of 20 to 220 Angstron and the total pore volume is 1.8 to 3 ml / g. 5. The porous clay mineral powder has a BET specific surface area of 70 to 400 m 2 / g, a bulk density of 0.5 g / ml or more, and an oil absorption of 150 ml / 100 g.
The refrigerating composition according to any one of claims 1 to 4, which is as follows. 6. The porous clay mineral is a layered clay mineral-based activated clay powder having a BET specific surface area of 300 m 2 /
g and a bulk density of 0.7 g / ml or less.
The refrigerating composition according to any one of the preceding claims. 7. The cooling agent composition according to claim 5, wherein the porous clay mineral is a chain-like viscous mineral-based sepiolite powder.