JPS6249193A - Manufacture of heat storage capsule - Google Patents

Abstract

PURPOSE:To improve the heat exchange performance by filling a silicon rubber capsule with a latent heat storage material. CONSTITUTION:A hollow annular nozzle operates in such a manner that a double fluid hardening type silicon rubber is continuously extruded through spinning holes 11 formed outside the nozzle and a latent heat storage material in a molten state is intermittently extruded by the opening or closing of a valve 18 through the spinning hole. The thus continuously extruded latent heat storage material filled encapsulated materials 13 are dipped in a water tank 14 of a constant temperature of approximately 80-100 deg.C for approximately seven minutes or more wherein silicon rubber is completely cured. By such operations, capsules 13 of a heat storage material, connected in a rosary state, are manufactured. That is, the capsules of the heat storage material consists of the capsule wall of silicon rubber and the latent heat storage material filled in the capsules by the intermittent extrusion. Since rubber parts in which the heat storage material is not filled form constricted parts, and these parts are cut later whereby individual heat storage material being encapsulated can be obtained.

Description

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

More specifically, it is related to the manufacturing method of a heat storage material capsule that is effectively used as a heat storage material used in a heat storage device. A commonly used method for increasing the exchange area is to house the heat storage material in a capsule and place the capsule in a heat storage tank. Capsules can be formed by filling five bags with heat storage material and squeezing the mouth to form a spherical or columnar shape, or by filling a circular or square cylindrical container with heat storage material and using both ends of the capsule. Those with occlusion 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. Since it cannot be manufactured, 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 is controlled by heat transfer, are both slow, and in some cases, it is difficult to absorb heat at a constant temperature, which is the most advantageous of latent heat storage. Since it makes it impossible to release heat, it becomes a fatal drawback when storing heat.

[Problem that the invention seeks to solve]

As a result of various studies in order to develop a new heat storage material for use in heat storage devices, etc. without causing these problems, the non-applicant has developed a method in which molten resin or spinning stock solution 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 spinning hole inside the spinning hole, and in the case of melt spinning using a molten resin, the coextrudate is immediately cooled, or in the case of dry-wet spinning using a spinning stock solution. It has been found that a hollow fiber whose hollow part is filled with a latent heat storage material, which is produced by allowing the coextrudate to fall naturally and then guiding it into a gelling solution of the spinning solution, is extremely effective (Unexamined Japanese Patent Publication No. Publication No. 58-163724).

However, it has since been found that the hollow fiber filled with the latent heat storage material manufactured in this manner has problems that still need to be improved.

That is, such hollow fibers are manufactured by a melt spinning method or a wet-dry 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 the same time (approximately 150 to 250°C), 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 interact with the latent heat storage material filled there. come into contact. Incidentally, inorganic hydrates, which have a large amount of latent heat storage and are useful latent heat storage materials for space heating and hot water supply, are easily soluble in water, and their molten liquid boils at 100°C or higher. In the proposed method, it was not possible to use an inorganic hydrate as a latent heat storage material.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, such Although this drawback can be avoided, the heat treatment to harden the coating layer must be carried out at a temperature of nearly 120 degrees Celsius, which imposes the restriction that heat storage materials that deteriorate at such temperatures cannot be used. .

The present inventor has improved the manufacturing method of hollow fibers filled with latent heat storage material, which is subject to these limitations, and has not only made it possible to use inorganic hydrates as the latent heat storage material, but also made it possible to use capsule-like fibers, which is a more preferable form than hollow fibers. He first proposed a heat storage material (Japanese Patent Application No. 59-24646).

This proposed heat storage material capsule is made by filling a silicone rubber capsule with a latent heat storage material.It is manufactured by filling a silicone rubber capsule with a latent heat storage material. After co-extruding the molten latent heat storage material from the holes, heating the outer silicone rubber layer of the coextruded latent heat storage material-filled hollow fiber to a semi-hardened state and cooling to solidify the internal latent heat storage material layer are sequentially performed. This is carried out by cutting the hollow fiber to a desired length, covering the cut surface with semi-cured silicone rubber, and then heating the semi-cured silicone rubber to its complete curing temperature.

In order to improve the heat exchange performance of heat storage material capsules manufactured by this manufacturing method, it is necessary to increase the surface area of the capsule relative to the amount of heat storage material filled. It was necessary to make the diameter smaller or the length shorter, which caused problems in terms of equipment and operation.

Therefore, the inventor of the present invention further investigated methods for improving this point, and as a result, by adopting the following method,
It has been found that such problems can also be effectively solved.

[Means for Solving the Problems] and [Operation] Therefore, the present invention relates to a method for producing a heat storage material capsule, and the heat storage material capsule is produced by injecting liquid curing type silicone from a spinning hole outside a hollow annular nozzle. By extruding the rubber continuously and intermittently extruding the molten latent heat storage material from the spinning holes inside the rubber, heating and hardening the Silico-2111 part, and then cutting it at the part that does not contain the heat storage material. It will be done.

In the present invention, a liquid curing type silicone rubber, preferably a two-component curing type silicone rubber, is used as the capsule wall material from the viewpoint of workability.

As such two-component curing type silicone rubber, various grades of Shin-Etsu Silicone LIMS (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 capsule container includes inorganic hydrates, such as sodium acetate trihydrate, disodium phosphate dodecahydrate, barium hydroxide octahydrate, and zinc nitrate.・Hexahydrate, nickel nitrate hexahydrate, sodium thiosulfate pentahydrate, etc. 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. 11 of the drawings is a schematic diagram showing one embodiment of a method for manufacturing a heat storage material capsule, and FIG. 2 is a sectional view of a hollow annular nozzle used therein.

Liquid or paste two-component curing silicone rubbers A and B are sent to mixer 3 via tanks 1 and 1' and metering pumps 2 and 2', respectively, where they are mixed and then passed through the silicone rubber inlet. 4 into a hollow annular nozzle 5.

On the other hand, the latent heat storage material tank 7 housed in the thermostatic chamber 6 together with this hollow annular nozzle receives the pressure of air 9 regulated by the pressure regulating valve 8, and the molten heat storage material charged therein is transferred to the latent heat storage material tank 7. It is designed to be fed into the hollow annular nozzle through the introduction port 10.

This hollow annular nozzle has two holes from the outer spinning hole 11.
A liquid curing type silicone rubber is continuously extruded, and a molten latent heat storage material is passed through a spinning hole 12 inside the valve 1.
It is made to extrude intermittently by opening and closing 8. The latent heat storage material-filled encapsulated material 13 intermittently coextruded in this way is then stored in a constant temperature water bath 1 at approximately 80 to 100°C.
4 for about 7 minutes or more, during which time the silicone rubber is completely cured.

Through such operations, heat storage material capsules 13 having a continuous shape are manufactured, the details of which are shown in FIG. 3 in cross section. That is, the heat storage material capsule is made of a silicone rubber capsule wall 15 and a latent heat storage material 16 filled into the capsule by intermittent extrusion. By cutting at this portion, individual heat storage material capsules can be obtained.

〔Effect of the invention〕

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

Moreover, according to the method of the present invention, by adjusting the nozzle diameter and the opening/closing time of the latent heat storage material supply valve, capsules of arbitrary dimensions can be manufactured. It can have a large heat transfer area relative to the amount of heat storage material filled in it, and therefore has excellent heat exchange performance.

〔Example〕

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 illustrated embodiment. 6 Two-component curing silicone rubber (Shin-Etsu Silicone KE 1)
925) are mixed in a mixer and introduced into the outer chamber of the hollow annular nozzle. On the other hand, sodium acetate trihydrate (melting temperature 58°C) as a latent heat storage material is introduced into the inner chamber of the hollow annular nozzle while being maintained in a constant temperature molten state of 80°C.

Two-component curing silicone rubber is 20an with a discharge pump.
Sodium acetate trihydrate was fed from the outer spinning hole (outer diameter 2.6 mm, inner diameter 1.0 mm) of the hollow annular nozzle while adjusting the discharge rate to a rate of 20 countries/min using an air pressure control valve. The spinning hole inside the hollow annular nozzle (diameter 1
．． 0 mm), respectively.

The intermittently coextruded latent heat 29 heat material-filled capsules were allowed to fall naturally at approximately 1 Oa11, then placed in a constant temperature water bath maintained at 80°C and left there for 2 hours to completely cure the silicone rubber layer. Ta. Thereafter, constrictions formed at approximately 301-degree intervals were cut to obtain heat storage material capsules.

The obtained silicone rubber capsule filled with sodium acetate trihydrate and having an outer diameter of about 3 mm had a silicone rubber layer on the capsule wall portion of about 0.8+ am and a fairly uniform wall thickness.

Example 2 In Example 1, disodium phosphate dodecahydrate (melting temperature 36°C) was used as the latent heat storage material, and the discharge interval of the 1M heat material was repeated by opening the valve for 4 seconds and closing it for 2 seconds.
A silicone rubber capsule filled with disodium phosphate dodecahydrate and having an outer diameter of about 3 mm and a length of about 15 m+* was produced.

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 hollow annular nozzle was maintained at 95°C. As a result, barium hydroxide octahydrate-filled silicone rubber capsules having an outer diameter of about 3+a and a length of about 30+e+a were manufactured.

Examples 4 to 5 In Example 1, zinc nitrate hexahydrate (melting temperature 36°C) or nickel nitrate hexahydrate (
A silicone rubber capsule filled with these latent heat storage materials was manufactured.

[Brief explanation of the drawing]

FIG. 1 is a schematic view showing one embodiment of a method for manufacturing a heat storage material capsule, and FIG. 2 is a sectional view of a hollow annular nozzle used therein. Moreover, FIG. 3 is a sectional view of the coextruded heat storage material capsule before cutting. (Explanation of symbols) 1...Two-component curing silicone rubber tank 3...
... Mixer 5 ... Hollow annular nozzle 6 ... Constant temperature bath 7 ... Latent heat storage material tank 11 ... Spinning hole 12 outside the nozzle ... Nozzle Spinning hole 13 inside... Latent heat storage material filled capsule 14...
Constant temperature water tank 15...Capsule wall 16...Filled latent heat storage material 17...Constriction 18...Opening/closing valve, agent

Claims (1)

[Claims] 1. Liquid curing silicone rubber is continuously extruded from the spinning holes on the outside of the hollow annular nozzle, and molten latent heat storage material is intermittently extruded from the spinning holes inside the hollow annular nozzle. A method for producing a heat storage material capsule, which comprises curing a portion by heating and then cutting at a portion that does not contain the heat storage material. 2. The method for producing a heat storage material capsule according to claim 1, wherein the liquid curing silicone rubber is a two-component curing silicone rubber. 3. Claim 1 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. 4. The method for producing a heat storage material capsule according to claim 1, wherein the silicone rubber portion is cured by heating in a constant temperature water bath located below the hollow annular nozzle.