JPS60169090A - Heat accumulating material capsule and manufacture thereof - Google Patents

Abstract

PURPOSE:To enable to manufacture encapsulated heat accumulating material by a method wherein liquid silicon rubber and molten latent heat accumulating material a re coextruded from the outside and inside spinning holes of a hollow and annular nozzle in the form of a hollow yarn, which is heated, cooled and cut in arbitrary lengths and then cut surfaces of which are covered with rubber and heated. CONSTITUTION:A hollow yarn spinning nozzle is equipped with a hollow and annular spinning holes, through the outside spinning hole 11 of which two-part hardening type silicon rubber and through the inside spinning hole 12 of which molten latent heat accumulating material are coextruded. The coextruded latent heat accumulating material-filled hollow yarn 13 is heated by means of a heater 14 up to 60-90 deg.C so as to turn the silicon rubber layer into semi-hardened state and cooled by means of a fan 15 or the like so as to set the inner latent heat accumulating material layer. After that, the yarn 13 is cut into chips having a length of 1-100cm. At this case, a capsule is formed, because the silicone rubber in semi-hardened state goes round the edge of the cut surface so as to cover said surface. The encapsulated objects are dipped in a constant temperature water bath having a temperature of 80-100 deg.C for about 7min or longer in order to completely harden the silicon rubber. Inorganic hydrate can be employed. In addition, continuous micro-capsulation is easily realized.

Description

[Detailed description of the invention] The present invention relates to a heat storage material capsule and a method for manufacturing the same.

More specifically, the present invention relates to a heat storage material capsule that is effectively used as a heat storage material used in a heat storage device, and a method for manufacturing the same.

Conventionally, when designing a heat storage device using a latent heat storage material, the general method of increasing heat exchange efficiency has been to house the heat storage material in a capsule and place this capsule in a heat storage tank. There is. Capsules can be made by filling a bag with heat storage material and squeezing the opening to make a spherical or columnar body, or by filling a heat storage material into a cedar or square-shaped cylindrical container. Those with both ends closed are used.

These heat storage material-filled capsules are manufactured through a capsule manufacturing process, a heat storage material filling process, and a capsule closing process at both ends, which not only requires a lot of effort, but also requires a lot of time and effort, and due to capsule manufacturing constraints, it is difficult to manufacture capsules that are too small. Therefore, there is also the problem that a large heat transfer area for heat exchange cannot be provided. The fact that the heat transfer area cannot be increased means that the heat absorption rate and heat release rate of the heat storage material, which are controlled by heat transfer, will both be slow, and in some cases, the heat at a constant temperature, which is the most advantageous of latent heat storage, will be slow. This makes it impossible to take out the heat, which is a fatal drawback when it comes to storing heat.

The present applicant has previously discovered that in order to avoid such problems, the heat storage material used in heat storage devices, etc. can be made by immediately cooling the coextrudate in the case of melt spinning using a new molten resin, and by immediately cooling the coextrudate. In the case of dry-wet spinning using a co-extrudate, a hollow fiber whose hollow part is filled with a latent heat storage material is extremely effective, as it is produced by letting the coextrudate fall naturally and then guiding it into a gelatinized spinning solution. (Japanese Unexamined Patent Publication No. 163724/1983).

However, it was subsequently discovered that the hollow fibers filled with the latent heat storage material produced in this manner had problems that still needed to be improved.

That is, such hollow fibers are manufactured by a melt spinning method or a dry-wet spinning method, and in the melt spinning method, a molten latent heat storage material is coextruded as a core liquid from the inside of a hollow annular nozzle. Due to the temperature of the molten resin coextruded at 171 degrees centigrade (approximately 150 to 250 degrees Celsius), there is a restriction that a heat storage material that deteriorates at such a temperature cannot be used.

In addition, in the dry-wet spinning method, fine pores are formed in the hollow fibers, so if water or an aqueous medium is used as a gelling bath, they will penetrate into the hollow fibers and the latent heat storage material filled therein. come into contact with. Incidentally, inorganic hydrates, which have a large amount of latent heat storage and are useful latent heat storage materials for heating, hot water supply, etc., are easily soluble in water, and their molten liquid Fiio.

Inorganic hydrates could not be used as latent heat storage materials in the proposed method because they boiled at temperatures above 7°C. However, as described in the above-mentioned patent publication, if the surface of the hollow fiber, especially the outer surface, is coated with a resin,
Although such drawbacks can be avoided, the heat treatment for curing the coating layer must be performed at a temperature close to 120°C, so such 1'K tA
A constraint arises in that heat storage materials that degrade with Bt cannot be used.

The present invention improves the manufacturing method of hollow fibers filled with latent heat storage material, which is subject to the following limitations. The preferred shape is a capsule-shaped heat storage f; the A size is A7.

Therefore, the present invention relates to a heat storage material capsule, and the heat storage material capsule is made of a silicone rubber capsule filled with a latent heat storage material. The present invention also relates to a method for manufacturing such a heat storage material capsule, in which a liquid curing type silicone rubber is spun from a spinning hole outside a hollow annular nozzle.
In addition, the latent heat storage material in a molten state is coextruded from the inner spinning hole (-1 Heating to semi-harden the outer silicone rubber layer of the coextruded hollow fiber filled with the latent heat storage material and solidifying the internal latent heat storage material layer. After sequential cooling, the hollow fiber is cut to a desired length, the cut surface is covered with semi-cured silicone rubber, and then heated to the complete curing temperature of the semi-cured silicone rubber.

In the present invention, hollow fibers are first spun from a liquid curing type silicone rubber, preferably a two-component curing type silicone rubber from the viewpoint of workability. As such two-component curing silicone rubber, various grades of Shin-Etsu Silicone Rubber MS (liquid injection molding silicone rubber system) manufactured by Shin-Etsu Chemical Co., Ltd. can be used, for example.

The latent heat storage material filled in the silicone rubber hollow fibers may include inorganic hydrates such as sodium acetate trihydrate, disodium phosphate dodecahydrate, barium hydroxide, etc.
Octahydrate, zinc nitrate hexahydrate, nickel nitrate hexahydrate, sodium thiosulfate pentahydrate, and the like are preferably used.

Here, a method for manufacturing a heat storage material capsule according to the present invention will be explained with reference to the drawings.

FIG. 1 of the drawings is a schematic diagram showing a method of manufacturing a heat storage material capsule, and FIG. 2 is a sectional view of a hollow annular nozzle used therein.

Two-component curing silicone rubbers A and Bti in liquid or paste form are sent to mixer 3 via tanks 1 and f and metering pump 2.2', respectively, where they are mixed and then transferred to silicone rubber inlet 4. frame) and is fed into the hollow fiber spinning nozzle 5.

On the other hand, seven latent heat storage material tanks housed in a constant temperature bath 6 together with this spinning nozzle receive the pressure of air 9 regulated by a pressure regulating valve 8, and the molten heat storage material charged therein is transferred to a heat storage material. [Inlet port] The material is fed into the spinning nozzle from O.

The hollow fiber spinning nozzle forms a hollow annular nozzle, and a two-component curing type silicone rubber is fed from the outer spinning hole 11, and a molten latent heat storage material is fed from the inner spinning hole 12. Each is coextruded. The co-extruded latent heat storage material-filled hollow fibers 13 have a temperature of about 60 to 90
The outer silicone rubber layer is heated to about .degree. Thereafter, the hollow fibers are cut into lengths of about 1 to 100 cm using a chopper 16 or the like.

Generally, when a chip is cut at right angles to the fiber direction, the semi-cured silicone rubber that forms its cylindrical outer circumferential surface (from liquid to highly viscous syrup-like state) wraps around the cut surface. , so a capsule is formed there. The encapsulated product is then immersed in a constant temperature water bath 17 at about 80 to 100° C. for about 7 minutes or more, where the silicone rubber is completely cured.

The heat storage material capsule 18 manufactured in this way, in which the silicone rubber capsule is filled with a latent heat filler, can use an inorganic hydrate, which is a latent heat storage material that is useful for heating, hot water supply, etc. The effect is that the microencapsulation can be carried out continuously and easily.

Next, the present invention will be explained with reference to examples.

Example 1 A heat storage material capsule was manufactured in the following manner according to the procedure shown in Figure 7.

2. Silicone rubber (4mm silicone K)
l! ! 1925)! (Mix the liquid and B liquid with a mixer and introduce it into the outer mold of the hollow fiber spinning nozzle.-
10,000, acetic acid as a latent heat storage material) IJum trihydrate
While keeping J (melting temperature 58°C) at a constant temperature of 80°C, it is placed in the inner mold of a nozzle for spinning intermediate yarn.

Two-component curing silicone rubber is 20cn with a discharge pump.
While adjusting the discharge gong to 1/min, the spinning hole (outer diameter 2,6111111 mm, inner diameter 1.0 mm) on the outside of the inner pot annular nozzle was used, and sodium acetate IJium trihydrate was supplied through the air pressure control valve. Again, each co-extrusion is carried out from the spinning hole (diameter 1.0111 il) inside the hollow annular nozzle while adjusting the discharge volume to 20 cm/min.

The coextrusion-spun hollow fiber filled with latent heat storage material was allowed to fall naturally for about 1 m, and then heated to 80°C.
00 cm through a tubular heater at a rate with a residence time of 5 minutes. At this time, the silicone rubber layer is in a semi-cured state and exhibits almost no fluidity. The hollow fiber that has passed through the tubular heater is air-cooled by a fan, thereby solidifying the latent heat storage material filled inside the hollow fiber. Thereafter, the hollow fiber was cut into a length of about 30 cm, and the cut surface was rounded and encapsulated with semi-cured silicone rubber. Since this silicone rubber capsule was in a semi-cured state, it was placed in a constant temperature water bath maintained at 80'C to completely cure the silicone rubber layer.

The obtained silicone rubber capsules filled with sodium acetate trihydrate and having an outer diameter of about 3 mm have a silicone rubber layer of about 0.8 mm.
It was a gourd and had a fairly uniform thickness.

Example 2 In Example 1, dinatophosphoric acid IJ was used as the latent heat storage material.
Um dodecahydrate (melting temperature 36°C) was cooled with water at 20°C after passing through a tubular heater, and hollow fibers filled with latent heat storage material were cut in water, with an outer diameter of about 3 tEM and a length of about 3 tEM. Approximately 200 n of disodium phosphate dodecahydrate filled silicone rubber capsules were prepared.

Example 3 In Example 1, barium hydroxide was used as the latent heat storage material.
Octahydrate (melting temperature 78°C) was used, but the temperature of the constant temperature bath containing the heat storage material and the spinning nozzle was maintained at 95°C. As a result, barium hydroxide octahydrate-filled silicone rubber capsules having an outer diameter of about 3 fi and a length of about 30 cn+ were manufactured.

Examples 4 to 5 In Example 1, zinc nitrate hexahydrate (melting temperature 36°C) or nickel nitrate hexahydrate (
(melting temperature of 54° C.) were used, and silicone rubber capsules filled with these latent heat storage materials were manufactured.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing one aspect of the method for manufacturing a heat storage material capsule, and FIG. 2 is a 10" side view of a hollow annular nozzle used therein. (Explanation of symbols) 1... ...Two-component curing silicone rubber tank 3.
...Mixer 5 ...Hollow annular nozzle for hollow fiber spinning 6 ...
... Constant temperature bath 7 ... Latent heat storage material tank 11 ... Spinning hole 12 outside the nozzle ...
・Spinning hole 13 inside the nozzle...Hollow fiber filled with latent heat storage material 14...Heater 15...Fan 16...Chopper 17...・Constant-temperature water tank 18...Thermal storage material Kabuchiru Patent attorney Yoshi 1) Toshio Figure 1 Figure 2 Procedural amendment document (1) June 18, 1980 Commissioner of the Patent Office Kazuo Wakasugi 1 Display of the case 2 Name of the invention A heat storage material capsule and its manufacturing method; 3 Relationship with the case by the person making the amendment Name of the patent applicant (438) Japan Oil Seal Industry Co., Ltd. 4 Agent (105) Address Shiba Daimon, Minato-ku, Tokyo 1-2-7 Ato Building 501
Insert the issue text. Note that if the cut surface is not completely covered with silicone rubber, the uncured silicone rubber 11 can be coated or dipped again on the cut surface to complete the coating. ”

Claims (1)

[Scope of Claims] 1. A heat storage material capsule formed by filling a latent heat storage material into a silicone rubber capsule. 2. The heat storage material capsule according to claim 1, wherein the silicone rubber capsule is a cylindrical body. 3. Claim 1 in which the latent heat storage material is an inorganic hydrate
The heat storage material capsule described in Section 1. 4. Co-extrude the liquid curing silicone rubber from the outer spinning hole of the hollow annular nozzle and the molten latent heat storage material from the inner spinning hole to form the outer silicone of the coextruded hollow fiber filled with the latent heat storage material. After heating the rubber layer to a semi-hardened state and cooling to solidify the internal latent heat storage material layer, the hollow fiber is cut to a desired length and the cut surface is held with semi-hardened silicone rubber. A method for producing a heat storage material capsule, which comprises heating to a complete curing temperature of cured silicone rubber +, yi. 5. The method for producing a heat storage material capsule according to claim 4, wherein the liquid curing silicone rubber is a two-component curing silicone rubber. 6. Claim 4 in which the latent heat storage material is an inorganic hydrate
A method for producing a heat storage material capsule as described in Section 1.