JPH05256549A - Thermal insulation cabinet and thermal insulation car - Google Patents

Abstract

PURPOSE:To provide a thermal insulator cabinet whose housing space for intended articles, such as vegetables and fruits and fishes is not narrowed with a coolant and excellent in terms of effective utilization of the housing space. CONSTITUTION:A thermal insulation cabinet is surrounded by shape holding bodies (1 and 2) which are a solid-state mixture of a hydrocarbon group heat storage component whose melting point ranges from 0 to 18 deg.C and an organic polymer. This insulated container is excellent in terms of heat storage quantities and capable of maintaining a cooling atmosphere for a long time, which is suitable to store vegetables and fruits or fishes at a low temperature or hold their freshness and being serviceable repeatedly with heat storage treatment. What is more, the shape holding bodies are excellent in terms of a holding power to keep a heat storage component and hence prevents the heat storage component from flowing out. It is also excellent in terms of vibration resistance. Even when it is applied to a thermal insulation vehicle or the like, the thermal insulation cabinet can withstand breakdown due to its strength.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention makes it possible to maintain the inside of a refrigerator in a cooling atmosphere of 0 to 18 ° C. through heat storage components.
The present invention relates to a refrigerating box and a refrigerating car that are excellent in space utilization efficiency.

[0002]

2. Description of the Related Art Conventionally, there has been a cool box such as a cooling box in which a cooling atmosphere made of a cooled solidified material of a heat storage material coated with ice or dry ice or a resin is put in an insulating box. Was known. However, since the coolant occupies a part of the space inside the heat insulation box, there is a problem that the space for storing the object such as fruits and vegetables is narrowed.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to develop a cool box which is excellent in effective utilization of the accommodation space without narrowing the accommodation space of the object with a cooling material.

[0004]

The present invention has a melting point of 0 to 1
The present invention provides a cool box characterized in that a shape-retaining body made of a solid mixture of a hydrocarbon-based heat storage component at 8 ° C. and an organic polymer is arranged around the shape-retaining body.

[0005]

[Function] By mixing a hydrocarbon-based heat storage component having a melting point of 0 to 18 ° C with an organic polymer, it has an excellent heat storage amount (heat of fusion) and is suitable for low-temperature storage and freshness preservation of fruits and vegetables. The shape-retaining body can be formed. Then, the shape-retaining body can be arranged around the cool box by a method of forming a wall surface by molding the shape-retaining body, and it is possible to prevent the accommodation space of the target object from being narrowed by the shape-retaining body which is a coolant.

[0006]

EXAMPLE The cold-storage box of the present invention is formed by arranging a shape-retaining body composed of a solid mixture of a hydrocarbon-based heat storage component having a melting point of 0 to 18 ° C. and an organic polymer around it. An example thereof is shown in FIG. Reference numeral 1 is a lid made of the shape retainer, and 2 is a storage container made of the shape retainer.

The hydrocarbon-based heat storage component used for forming the shape retainer has a melting point of 0 to 18 ° C., preferably 0 to 10 ° C., from the viewpoint of low temperature storage and freshness preservation of fruits and vegetables. Examples of the hydrocarbon heat storage component include those containing n-paraffin having 14 to 16 carbon atoms or n-α-olefin having 16 to 18 carbon atoms as a main component. Such heat storage components may be used alone or as a mixture of two or more kinds.

The above-mentioned n-paraffin or n-α-olefin may contain impurities within a range not impairing the melting point of 0 to 18 ° C. Generally, those having a purity of 50% or more, preferably about 90% or more, are used in terms of the amount of heat storage. Therefore, a commercially available commercial product can be used as it is. Examples of the impurities include paraffins having 12 or 18 carbon atoms and 14 carbon atoms.
And α-olefins such as and 20, branched olefins, and paraffin. Therefore, the above n-paraffin and n
The -α-olefin may be prepared by an appropriate method.

Examples of the preparation of n-paraffins include a method of recovering from petroleum fractions such as naphtha, kerosene, and light oil, a method of separately recovering from by-products during the synthesis of polyethylene, and a method of recovering polyethylene and crosslinked polyethylene from waste. There is a method of separately collecting the. The above-mentioned petroleum-based fraction can be recovered by, for example, a gas phase method (ISOS
IV method, BP method, etc.), liquid phase method (MOLEX method), method using urea (NUREX method, EDELEANU method, etc.), and the like.

On the other hand, the n-α-olefin can be prepared by an appropriate method such as ethylene low polymerization method. As the n-α-olefin, those which do not contain aromatic compounds, naphthene compounds, diolefins and the like as impurities and have a small content of inner olefins such as β and γ are preferably used.

In the present invention, the melting point of the heat storage component is D
It means the peak endothermic temperature in the endothermic measurement using SC (Differential Scanning Calorimeter) to increase the temperature from −20 ° C. (solidified state) to 25 ° C. (liquid state) at a rate of 2 ° C./min.

The shape-retaining body can be formed by mixing a hydrocarbon-based heat storage component and an organic polymer into a solid form. In that case, a mixing method by mechanical means such as stirring treatment, mixing treatment, and kneading treatment is preferable. According to the mixing method by mechanical means, even if a large amount of hydrocarbon-based heat storage components of 300 to 2000 parts by weight per 100 parts by weight of the organic polymer is mixed, the moldability is excellent and the heat storage components migrate (bleed). You can easily get the one that is difficult and sticky.

As the organic polymer, any suitable one that maintains a solid state in the operating temperature range can be used, and one having rubber-like properties is preferable. Among other things, the backbone is essentially hydrocarbon and other components in the backbone (eg O, N,
Si, halogen, etc.) content is 10 wt% or less, especially 5
Hydrocarbon-based polymers of up to wt% are preferably used. Hydrocarbon-based polymers such as olefin-based polymers, thermoplastic elastomers, and hydrocarbon-based rubbers are particularly preferable.

The organic polymer may be used alone or in combination of two or more, and may be a crosslinked product. The crosslinking can be carried out by an appropriate method such as a chemical crosslinking method using an added crosslinking agent, a water crosslinking method using a silane graft, an irradiation crosslinking method, or the like, at an appropriate stage during mixing or after mixing. The degree of cross-linking is 1% by weight or more, and especially 2% by weight or more in terms of gel fraction (JIS C 3005) based on the mixture with the heat storage component from the viewpoints of preventing outflow of the heat storage component in a liquid state and maintaining shape. preferable.

Specific examples of the olefin-based polymer include homopolymers of α-olefins such as polymethylene, polyethylene and polypropylene, copolymers of olefins with each other, α-olefin and vinyl acetate, ethyl acrylate, and other types such as ethyl methacrylate. Examples thereof include copolymers with monomers and their lightly halogenated polymers, and the crystallinity thereof is not particularly limited.

Specific examples of the above-mentioned thermoplastic elastomer include any of known substances such as styrene type, olefin type, urethane type and ester type. For example, from room temperature to 10 ° C above the freezing point of the heat storage component used together, Especially 20
A material having rubber elasticity at least in a use temperature range such as a temperature range higher by ℃ is preferably used.

Specific examples of the hydrocarbon rubber include natural rubber, styrene / butadiene rubber, butyl rubber, isoprene rubber, ethylene / propylene rubber, ethylene / propylene / diene rubber, ethylene / vinyl acetate rubber and ethylene / ethyl acrylate rubber. can give.

The mixing by mechanical means is, for example, a method in which one of the melts is swollen or dissolved in one, and the other is stirred and mixed, or both are heated to be in a fluid state or melted, and they are kneaded or stirred and mixed. For example, 5
A suitable method such as a method of kneading with a kneader heated to 0 to 250 ° C. may be used.

For kneading, a conventional mixer such as a two-roll mill, a Banbury mixer, an extruder or a twin-screw kneading extruder can be used. It is preferable that the mixed state is as uniform as possible, but in general, the mixed state is such that it can be judged visually that the mixed state is uniform for 1 to 150 minutes.

The obtained solid mixture is a powder such as pellets or granules, as well as a pouring method, a pressing method,
A shape-retaining body can be obtained by processing into an arbitrary form such as a sheet, a plate, or a honeycomb body by an appropriate method such as an extrusion molding method or an injection molding method.

The solid mixture may contain various additives, antioxidants, colorants, pigments, antistatic agents, mildew-proofing agents, flame retardants, rodent-proofing agents, heat transfer materials such as metals and carbon, etc. Various compounding agents can be added.

The solid mixture or shape-retaining material is foamed with gas or a foaming agent, has a low specific gravity by adding a balloon such as shirasu balloon, or has an inorganic high-density filler such as metal or ceramic. It is also possible to adjust the specific gravity by increasing the specific gravity.

It is also possible to adopt a reinforcing form by filling organic fibers or inorganic fibers or using a support such as a string, a wire, a non-woven fabric, a woven fabric or a net. Further, a soaking layer made of a heat conductive substance such as metal may be added, or a plastic sheet or a heat insulating material may be coated.

When forming the cool box, a shape-retaining body having an appropriate shape may be arranged around it. As an example, see FIG.
A method of forming a container such as a shape retainer molded into a plate as described above, a plate or sheet inside or outside a lid or a container formed of an appropriate material such as a heat insulating material, or inside (sandwich form) The method of arranging the shape-retaining body molded in 1 above, the method of filling and arranging the shape-retaining body formed in a granular shape or the like inside the double-structured lid or the container.

The cold storage of the present invention is used for various cold storage systems by utilizing the endothermic action of external heat when the hydrocarbon-based heat storage component in the shape retainer is cooled and solidified (solidified) and the solidified product is melted. You can Therefore, the cold storage of the present invention,
It can be preferably used for forming a cool container, a cooling box, and the like.

The hydrocarbon-based heat storage component can be cooled and solidified by an appropriate method such as cooling in a freezing room or a refrigerating room, cooling through ice or dry ice, cooling through a refrigerator, and the like. If the cool box is an assembly method of a shape retainer consisting of a small size plate via a mounting frame, or if the shape retainer is formed as granules or sheets so that it can be removed from the main body, a home freezer It is also possible to achieve cooling and solidification of the shape retainer (heat storage component) in a refrigerator.

The cold storage of the present invention can also be preferably used for forming a cold storage vehicle. That is, the cool box of the present invention can be loaded on the bed of a car as a cool container or the like,
As illustrated in FIG. 2, it can be preferably used for forming a cold storage vehicle 3 equipped with such a cold storage as a luggage storage room 4 in a freight vehicle.

In the above case, the form of the baggage accommodating chamber or the cooling and solidifying method of the hydrocarbon heat storage component can be based on the above-described method such as the method of forming the inner wall by the shape retainer formed on a plate or the like. It is also possible to adopt a cooling and solidifying method of a heat storage component during traveling through a vehicle-mounted power source such as DC 24V or 12V and a refrigerator. In addition, for cooling and solidification of the heat storage component,
There is also an advantageous method of utilizing surplus power at night.

Example 1 100 parts of n-tetradecane (containing pentadecane, main impurities: tridecane, measured by gas chromatography, the same applies hereinafter) having a purity of 95% and thermoplastic elastomer (shell chemical company) Made, Clayton G1
650 (the same applies hereinafter) and 5 parts of polyethylene A (density 0.935 g / cm ³ , MI 2 g / 10 min) under heating and melting, and an antioxidant (2,2,4-trimethyl-1,2).
A polymer mixture of dihydroquinoline (the same applies hereinafter) was mixed with stirring to obtain a solid mixture.

Next, the above solid mixture is extruded to form a plate (shape retainer) having a thickness of 14 mm, which has a thickness of about 10
mm styrene foam container with lid (H12cm × W21cm
X L27 cm) was adhered to the inner bottom surface to obtain a cool box.

Example 2 100 parts of a hydrocarbon heat storage component containing 53% by weight of n-pentadecane, 35% by weight of n-tetradecane, and 9% by weight of n-hexadecane, and 15 parts of a thermoplastic elastomer.
Polyethylene B (Density 0.925g / cm ³ , MI 10g
/ 10 minutes, the same hereinafter) 5 parts with stirring under heating and melting together with 0.2 parts of an antioxidant to obtain a solid mixture, which was used to obtain a shape-retaining body and a cold store according to Example 1.

Example 3 40 parts of 95% pure n-tetradecane, 60 parts of 98% pure n-hexadecane (containing n-tetradecane, the same applies hereinafter), 15 parts of thermoplastic elastomer and 5 parts of polyethylene B were heated. Stir-mix under melting with 0.2 parts of antioxidant to give a solid mixture which was used in Example 1
According to the above, a shape retainer and a cold storage were obtained.

Example 4 20 parts of n-tetradecane having a purity of 95%, 80 parts of n-hexadecane having a purity of 98%, and thermoplastic elastomer 1
5 parts and 5 parts of polyethylene B were mixed under heating with 0.2 part of an antioxidant with stirring to obtain a solid mixture, which was used to obtain a shape-retaining body and a cold store according to Example 1.

Example 5 50 parts of n-hexadecene-1 (containing n-octadecene-1, main impurity: tetradecene-1) having a purity of 92%,
90% pure n-octadecene-1 (containing n-hexadecene-1, main impurities: eicosene-1, the same applies hereinafter) 5
0 part, 15 parts of a thermoplastic elastomer, and 5 parts of polyethylene B were stirred and mixed with 0.2 part of an antioxidant while being heated and melted to obtain a solid mixture, which was used to prepare a shape retention body and cold insulation according to Example 1. I got a warehouse.

Example 6 N-octadecene-1 having a purity of 90%: 100 parts, thermoplastic elastomer 15 parts, and polyethylene B 5 parts were stirred and mixed with 0.2 part of an antioxidant under heating and melting to obtain a solid mixture. According to Example 1, a shape-retaining body and a cold storage were obtained.

Comparative Example 1 A container with a lid made of foamed styrene and having a thickness of about 20 mm (H12 cm)
(× W21 cm × L27 cm) was used as a cold storage as it was.

Comparative Example 2 n-tetradecane having a purity of 95% was used as it was. Since such n-tetradecane is liquid at room temperature (23 ° C.), a shape-retaining body and a cool box could not be obtained according to Example 1.

Evaluation Test The following characteristics of the shape retention body obtained in Example and the heat storage component of Comparative Example 2 were examined.

Melting point The peak endothermic temperature in a temperature range showing an endothermic amount of 20 cal / g or more was investigated by raising the temperature from DSC to -20 ° C to 25 ° C at a rate of 2 ° C / min.

Amount of heat storage Measured according to JIS K7122.

Bleed property After the shape-retaining body was allowed to stand at room temperature for 7 days, it was examined whether or not the heat storage component oozes out.

Shape Retention A solid mixture of 1 cm square block was allowed to stand at room temperature for 7 days, and then the change in shape was examined, and those having almost the original shape were evaluated as good, and those having flow or shape change were evaluated as defective. ..

Cold Storage The cold storage obtained in Example and Comparative Example 1 was left in a freezer at 0 ° C. for 8 hours and then taken out at room temperature (20 ° C., 65% RH).
It was left to stand and the change in the temperature inside the chamber with time was examined.

The above results are shown in Table 1.

[Table 1]

[0045]

In the cold storage box of the present invention, the shape-retaining body containing the heat storage component having a melting point of 0 to 18 ° C. is arranged around the wall surface or the like, so that the inside of the cold storage box, which is the storage space for the object, is narrowed by the coolant. In addition, the heat storage component has an excellent heat storage amount, and the inside of the refrigerator can be kept in a cooling atmosphere suitable for low temperature storage of fresh fruits and fish or keeping freshness for a long time, and it can be used repeatedly by heat storage. is there. Further, the shape-retaining body is excellent in holding power of the heat storage component to prevent the heat storage component from flowing out, and is also excellent in vibration resistance and the like, and is excellent in strength even when applied to a cold storage vehicle or the like, and is hard to break.

[Brief description of drawings]

FIG. 1 is a sectional view showing an embodiment of a cool box.

FIG. 2 is a partial cross-sectional explanatory view showing an embodiment of a cold insulation vehicle.

[Explanation of symbols]

 1: Lid 2: Storage container 3: Cold storage vehicle 4: Luggage storage room

Claims (2)

[Claims] 1. A cool box characterized in that a shape-retaining body made of a solid mixture of a hydrocarbon-based heat storage component having a melting point of 0 to 18 ° C. and an organic polymer is arranged in the periphery. 2. A cold storage vehicle, comprising the cold storage according to claim 1.