JPH1025360A - Cellular heat insulating material, production of the same and heat insulating box body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a heat insulating material and a heat insulating box body having an excellent heat insulating performance by removing carbon dioxide gas at the inside of cells in a cellular heat insulating material with an adsorption by an alkali metal hydroxide or an alkaline earth metal hydroxide, and further removing water generated by a side reaction of the adsorption reaction of carbon dioxide gas with a water adsorbing material coated with a resin membrane so as to fill the inside of cells by a vaporizable foaming agent having a low gas heat conductivity. SOLUTION: This cellular heat insulating material is constituted by a cellular polyurethane resin composition dispersed with either of an alkali metal carbonate or an alkaline earth metal carbonate 7 produced respectively by the reaction of an alkali metal hydroxide or an alkaline earth metal hydroxide with carbon dioxide and a water absorbing agent 10 consisting of a water adsorbing material 8 containing water and coated with a resin membrane 9, and having independent cells 5 filled with a vaporizable foaming agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamed heat insulating material for use in refrigerators and freezers, a method for producing the foamed heat insulating material, and
The present invention relates to a heat insulating box filled with a foamed heat insulating material.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of energy saving, there has been a need to reduce the thermal conductivity of a foamed heat insulating material and improve the heat insulating property.
C), and ozone depletion by hydrochlorofluorocarbon (hereinafter referred to as HCFC), and
Environmental problems such as global warming are attracting attention, and solving them is an extremely important theme.

[0003] Therefore, in producing rigid urethane foam, which is a typical foamed heat insulating material, CFC and
For the purpose of reducing the amount of HCFC used, various efforts have been made for foaming with hydrofluorocarbons (HFCs), which have no effect on ozone depletion, and hydrocarbons (HCs), which have little effect on global warming. Is being considered.

[0004] Basically, in order to improve the heat insulation performance of rigid urethane foam, it is important to reduce the gas thermal conductivity of the gas components in the fame bubbles. Efficient means have been to remove the high rate carbon dioxide gas and fill it with a volatile blowing agent.

On the other hand, a reactive foaming agent such as water and an organic polyether are used for the purpose of reducing the amount of the volatile foaming agent used, the problem of compatibility between the foaming agent and raw material components, and the improvement of various physical properties of the foam. It is essential to use carbon dioxide gas generated by the reaction with the isocyanate as a foaming agent component.

However, in such a configuration, since the carbon dioxide gas having a high gas thermal conductivity remains in the cells of the foamed heat insulating material, the heat insulating performance of the foamed heat insulating material becomes poor. For example, Japanese Patent Application Laid-Open No.
As disclosed in JP-A-322166, a method of removing a carbon dioxide component with a carbon dioxide adsorbent has been proposed. That is, an adsorbent consisting of an alkali metal hydroxide having excellent carbon dioxide adsorption performance is added and mixed in the raw material in advance, the generated carbon dioxide is adsorbed and removed by the adsorbent, and the bubbles are filled with a foaming agent gas. This is characterized by improving the heat insulation performance.

[0007]

However, in the structure used in Japanese Patent Application Laid-Open No. 6-322166, the adsorbent composed of an alkali metal hydroxide or the like is expressed by the following formula in the reaction process for adsorbing carbon dioxide gas. Water is formed as a by-product as shown.

[0008]

Embedded image

That is, the carbon dioxide gas inside the closed cells of the foamed heat insulating material is adsorbed and removed by an adsorbent composed of an alkali metal hydroxide or the like, and the inside of the closed cells is substantially a volatile foaming agent having a low thermal conductivity. Can be increased, but at the same time the water produced as a by-product diffuses into the closed cells until a certain vapor pressure is reached. As a result, the gas component inside the closed cells of the foamed insulating material has a very high gas thermal conductivity of water existing as a gas component,
It is conceivable that a sufficient effect of reducing the gas thermal conductivity cannot be exerted.

Accordingly, carbon dioxide in the foamed heat insulating material is adsorbed and removed by a carbon dioxide adsorbent such as an alkali metal hydroxide, and water produced as a side reaction does not affect the thermal conductivity. There was a problem in obtaining a foam heat insulating material having heat insulating performance and a heat insulating box.

SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a foamed heat insulating material having excellent heat insulating performance by quickly adsorbing and removing carbon dioxide gas in bubbles of a foamed heat insulating material and reacting and fixing water generated as a side reaction. It is an object of the present invention to provide a material and a manufacturing method thereof.

Insulation box having excellent heat insulation performance by quickly adsorbing and removing carbon dioxide gas in bubbles of the foam heat insulation material and filling with a foam heat insulation material for reacting and fixing water generated as a side reaction. It is intended to provide the body.

[0013]

The foam insulation of the present invention comprises:
Consists of a foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, at least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate, and a water-containing organic or inorganic compound. And a water adsorbent in which a water absorbent material is coated with a resin film.

The present invention is further characterized in that the carbonate is coated with a resin film. Further, the present invention is characterized in that the carbonate is contained inside the film of the moisture adsorbent in which the resin film is coated with a water-absorbing substance made of an organic or inorganic compound containing water.

Further, the water-absorbing substance comprising at least one organic or inorganic compound containing water is an alkali metal hydroxide.

According to the present invention, a foamed heat insulating material having excellent heat insulating performance is obtained, in which carbon dioxide in the cells of the foamed heat insulating material is adsorbed and removed, and water generated during the carbon dioxide gas adsorption reaction does not adversely affect the heat insulating performance. Can be

The method for producing a foamed heat insulating material of the present invention is characterized in that a polyol, a foam stabilizer, a catalyst, water, a volatile foaming agent, and a polyisocyanate are mixed with an alkali metal hydroxide or an alkaline earth metal hydroxide. A water absorbing agent coated with a resin film containing a water-absorbing substance made of an organic or inorganic compound is mixed and foamed, and carbon dioxide gas generated by the reaction of water and polyisocyanate inside closed cells, and a volatile foaming agent Forming a foamed polyurethane resin composition comprising: forming a carbonate by adsorbing carbon dioxide gas in the closed cells of the foamed polyurethane resin composition to form a carbonate, wherein the hydroxide is substantially volatile. The step of filling with a foaming agent, and the water generated when the hydroxide adsorbs carbon dioxide gas in the closed cells of the foamed polyurethane resin composition comprises an organic or inorganic compound. In which a step that is absorbed by the water absorbent coated with the aqueous material with a resin film.

Further, the present invention is characterized in that the hydroxide is previously coated with a resin film.

Further, the present invention is characterized in that the hydroxide is contained inside the film of the moisture adsorbing material in which the resin film is coated with a water-absorbing substance composed of at least one of organic and inorganic compounds.

Further, the water-absorbing substance comprising at least one of an organic or inorganic compound containing water is an alkali metal hydroxide.

According to the present invention, it is possible to manufacture a foamed heat insulating material having excellent heat insulating performance by adsorbing and removing carbon dioxide gas in the bubbles of the foamed heat insulating material and preventing moisture generated during the carbon dioxide gas adsorption reaction from affecting the heat insulating performance. A method can be provided.

The heat insulating box according to the present invention is characterized in that a space formed by a first wall member, a second wall member, the first wall member, and the second wall member has a volatile property. A foamed polyurethane resin composition having closed cells filled with a foaming agent is filled, and the resin composition contains an alkali metal carbonate or an alkaline earth metal carbonate and a water-absorbing organic or inorganic compound containing water. It is characterized by including a moisture adsorbent in which a substance is covered with a resin film.

Further, the present invention is characterized in that the carbonate is coated with a resin film. Further, the present invention is characterized in that the carbonate is contained inside the film of the moisture adsorbent in which the resin film is coated with a water-absorbing substance made of an organic or inorganic compound containing water.

Further, the present invention is characterized in that the hydroxide is contained in the inside of the moisture adsorbent film in which the resin film is coated with a water-absorbing substance comprising at least one of an organic or inorganic compound.

Further, the water-absorbing substance comprising at least one of an organic or inorganic compound containing water is an alkali metal oxide.

According to the present invention, there is provided a foamed heat insulating material having excellent heat insulating performance, in which carbon dioxide in bubbles of the foamed heat insulating material is adsorbed and removed, and water generated during the carbon dioxide gas adsorption reaction does not adversely affect the heat insulating performance. It is possible to obtain a high-performance heat insulating box provided.

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The foamed heat insulating material according to the first aspect of the present invention comprises a foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, and comprises an alkali metal carbonate or alkaline earth. It is characterized in that at least one carbonate of a metal carbonate and a moisture adsorbent in which a water-absorbing substance composed of an organic or inorganic compound containing moisture is coated with a resin film are included, and foaming is performed. A foamed heat insulating material excellent in heat insulation performance is obtained in which carbon dioxide gas in the bubbles of the heat insulation material is adsorbed and removed, and moisture generated during the carbon dioxide gas adsorption reaction does not adversely affect the heat insulation performance.

According to the above configuration, since the water-absorbing substance made of an organic or inorganic compound added as a raw material is covered with the resin film, it does not adsorb the reactive foaming agent during the production process of the foamed heat insulating material. It does not affect the urethane reaction. Further, the alkali metal hydroxide or the alkaline earth metal hydroxide has a low activity with respect to the reactive blowing agent, and does not inhibit the generation of carbon dioxide gas by the reaction between the reactive blowing agent and the polyisocyanate. In addition, since the reaction between the alkali metal hydroxide or the alkaline earth metal hydroxide and the carbon dioxide gas proceeds more slowly than the reaction for generating the carbon dioxide gas, the generated carbon dioxide gas contributes to the formation of bubbles in the foamed heat insulating material. It becomes possible.

On the other hand, the alkali metal hydroxide or the alkaline earth metal hydroxide reacts with the carbon dioxide gas remaining inside the bubbles after the foamed heat insulating material is formed to form a carbonate.
This makes it possible to substantially fill the gas components remaining inside the closed cells with the volatile foaming agent.

Further, the water adsorbent adsorbs water generated as a by-product by the reaction between the alkali metal hydroxide or the alkaline earth metal hydroxide and carbon dioxide. Thereby, the ratio of the volatile foaming agent in the gas component remaining inside the cells is further increased, and the gas thermal conductivity inside the closed cells of the foamed heat insulating material can be improved.

The foam insulating material according to the second aspect of the present invention comprises:
It is characterized in that the carbonate is coated with a resin film, the carbon dioxide gas in the bubbles of the foamed heat insulating material is adsorbed and removed, and moisture generated during the carbon dioxide adsorption reaction has a bad influence on the heat insulating performance. No foam insulation material with excellent heat insulation performance is obtained.

According to the above configuration, since the water-absorbing substance composed of an organic or inorganic compound added as a raw material is covered with the resin film, it does not adsorb the reactive foaming agent during the production process of the foamed heat insulating material. It does not affect the urethane reaction. Further, the alkali metal hydroxide or the alkaline earth metal hydroxide has a low activity with respect to the reactive blowing agent, and does not inhibit the generation of carbon dioxide gas by the reaction between the reactive blowing agent and the polyisocyanate. In addition, since the reaction between the alkali metal hydroxide or the alkaline earth metal hydroxide and the carbon dioxide gas proceeds more slowly than the reaction for generating the carbon dioxide gas, the generated carbon dioxide gas contributes to the formation of bubbles in the foamed heat insulating material. It becomes possible.

The carbonate of an alkali metal or the carbonate of an alkaline earth metal is covered with a resin film, and the carbon dioxide adsorption reaction proceeds more slowly after the foam is cured. Swelling of the foam due to occurrence is suppressed.

The foam insulating material according to the third aspect of the present invention comprises:
It is characterized in that the carbonate is contained in the inside of the film of the moisture adsorbent in which the water-absorbing substance composed of the organic or inorganic compound containing water is covered with the resin film, A foam heat insulating material excellent in heat insulation performance is obtained, in which gas is adsorbed and removed and moisture generated during the carbon dioxide gas adsorption reaction does not adversely affect heat insulation performance.

According to the above configuration, since the water-absorbing substance made of an organic or inorganic compound added as a raw material is covered with the resin film, it does not adsorb the reactive foaming agent during the production process of the foamed heat insulating material. It does not affect the urethane reaction. Further, the alkali metal hydroxide or the alkaline earth metal hydroxide has a low activity with respect to the reactive blowing agent, and does not inhibit the generation of carbon dioxide gas by the reaction between the reactive blowing agent and the polyisocyanate. In addition, since the reaction between the alkali metal hydroxide or the alkaline earth metal hydroxide and the carbon dioxide gas proceeds more slowly than the reaction for generating the carbon dioxide gas, the generated carbon dioxide gas contributes to the formation of bubbles in the foamed heat insulating material. It becomes possible.

Further, the water-absorbing substance is present in the vicinity of the reaction field of the carbon dioxide gas adsorption reaction, and is capable of quickly adsorbing and removing water, which is a factor of the adiabatic performance deterioration generated by the side reaction, and has a thermal conductivity. The effect of reducing the rate appears early.

The foam insulation according to the fourth aspect of the present invention comprises:
The water-absorbing substance is characterized by being an alkali metal hydroxide.The carbon dioxide gas in the bubbles of the foamed heat insulating material is adsorbed and removed, and the moisture generated during the carbon dioxide adsorption reaction has a bad influence on the heat insulating performance. A foam heat insulating material which does not affect and has excellent heat insulating performance can be obtained.

With the above-described structure, the alkali metal hydroxide quickly adsorbs and removes carbon dioxide gas and water, which is a factor of lowering the heat insulation performance generated as a by-product of the reaction between the carbon dioxide gas and the hydroxide. In addition, it is not necessary to newly add another solid component as a water-absorbing substance to the resin, so that the amount of the solid substance can be reduced, and the effect of further reducing the thermal conductivity can be obtained.

The method for producing a foamed heat insulating material according to claim 6 of the present invention is characterized in that a polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, and a polyisocyanate are added to an alkali metal hydroxide or At least one hydroxide of an alkaline earth metal hydroxide and a water absorbent adsorbed on a resin film with a water-absorbing substance comprising at least one organic or inorganic compound are mixed and foamed, and water is contained inside the closed cells. Forming a foamed polyurethane resin composition containing a carbon dioxide gas generated by the reaction of a polyisocyanate and a volatile foaming agent, and the hydroxide adsorbs carbon dioxide gas in closed cells of the foamed polyurethane resin composition. Forming a carbonate, and substantially filling the inside of the closed cells with a volatile foaming agent; and forming the hydroxide in the closed cells of the foamed polyurethane resin composition. Moisture generated when the acid gas is adsorbed is absorbed by a moisture adsorbent coated with a water-absorbing substance composed of at least one organic or inorganic compound with a resin film. A foamed heat insulating agent having excellent heat insulation performance is obtained, in which carbon dioxide gas in the inside is adsorbed and removed, and moisture generated during the carbon dioxide gas adsorption reaction does not adversely affect the heat insulation performance.

A method for producing a foamed heat insulating material according to a seventh aspect of the present invention is characterized in that the hydroxide is previously coated with a resin film, and the carbonate in the foam of the foamed heat insulating material is formed. A foam heat insulating material excellent in heat insulation performance is obtained, in which gas is adsorbed and removed and moisture generated during the carbon dioxide gas adsorption reaction does not adversely affect heat insulation performance.

According to the above structure, the alkali metal hydroxide or alkaline earth metal hydroxide is covered with the resin film, and the carbon dioxide adsorption reaction proceeds more slowly after the foam is cured. Swelling of the foam due to the generation of moisture at the time is suppressed.

[0042] In the method for producing a foamed heat insulating material according to claim 8 of the present invention, the inside of the moisture adsorbent film in which the hydroxide is coated with a resin film of a water-absorbing substance comprising at least one of an organic or inorganic compound. It is characterized by being included in, the carbon dioxide gas in the bubbles of the foam insulation is adsorbed and removed,
In addition, a foamed heat insulating material excellent in heat insulation performance can be obtained in which moisture generated during the carbon dioxide adsorption reaction does not adversely affect the heat insulation performance.

With the above structure, the water-absorbing substance is present in the vicinity of the reaction field of the carbon dioxide gas adsorption reaction, and can quickly adsorb and remove water, which is a factor of the adiabatic performance deterioration generated by the side reaction. The effect of reducing the conductivity appears at an early stage.

[0044] A method of manufacturing a foamed heat insulating material according to a ninth aspect of the present invention is characterized in that the water-absorbing substance is an alkali metal hydroxide, and the carbon dioxide gas in the foam of the foamed heat insulating material is provided. Is obtained, and moisture generated during the carbon dioxide gas adsorption reaction does not adversely affect the heat insulating performance, whereby a foamed heat insulating material having excellent heat insulating performance can be obtained.

With the above structure, the alkali metal hydroxide quickly adsorbs and removes carbon dioxide gas and water which is a factor of lowering the heat insulation performance generated as a by-product of the reaction between the carbon dioxide gas and the hydroxide. In addition, it is not necessary to newly add another solid component as a water-absorbing substance to the resin, so that the amount of the solid substance can be reduced, and the effect of further reducing the thermal conductivity can be obtained.

The heat insulation box according to claim 10 of the present invention is
A first wall member, a second wall member, and the first wall member,
And, in the space formed by the second wall member,
Filled with a foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, and in the resin composition, an alkali metal carbonate, and an alkaline earth metal carbonate, and an organic or inorganic compound containing water Characterized in that it contains a water adsorbent coated with a resin film with a water-absorbing substance consisting of at least one of the following, wherein carbon dioxide in the bubbles of the foamed heat insulating material is adsorbed and removed, and at the time of carbon dioxide adsorption reaction An excellent foam insulation material in which the generated moisture does not adversely affect the heat insulation performance can be obtained.

The heat insulating box according to claim 11 of the present invention comprises:
It is characterized in that the carbonate is coated with a resin film, the carbon dioxide gas in the bubbles of the foamed heat insulating material is absorbed and removed, and the water generated during the carbon dioxide gas adsorption reaction does not adversely affect the heat insulating performance. Thus, a foamed heat insulating material having excellent heat insulating performance can be obtained.

The heat insulation box according to claim 12 of the present invention comprises:
The carbonate is characterized in that the water-absorbing substance comprising at least one of an organic or inorganic compound containing water is contained in the film of the moisture adsorbing material coated with the resin film, and the bubbles of the foamed heat insulating material are formed. A foamed heat insulating material having excellent heat insulation performance is obtained, in which carbon dioxide gas inside is adsorbed and removed, and moisture generated during the carbon dioxide gas adsorption reaction does not adversely affect the heat insulation performance.

The heat-insulating box according to claim 13 of the present invention comprises:
The water-absorbing substance is characterized by being an alkali metal hydroxide.The carbon dioxide gas in the bubbles of the foamed heat insulating material is adsorbed and removed, and the moisture generated during the carbon dioxide adsorption reaction has a bad influence on the heat insulating performance. A foam heat insulating material which does not affect and has excellent heat insulating performance can be obtained.

Hereinafter, the embodiment will be described with reference to FIGS.
This will be described with reference to FIG. FIG. 1 is a partially cutaway perspective view of a heat insulating box according to an embodiment of the present invention.
Denotes a heat insulating box, and a polyurethane resin composition is used to fill a space formed by a first wall member 2 which is a vacuum formed body of an ABS resin composition and a second wall member 3 formed by processing a steel plate. Is filled and buried.

(Embodiment 1) The foam insulation 4 in Embodiment 1 will be described with reference to FIG.
The closed cell 5 is filled with a volatile foaming agent. The closed cell 5 contains an alkali metal carbonate or an alkaline earth metal carbonate 7 formed by reacting an alkali metal hydroxide or an alkaline earth metal hydroxide with carbon dioxide gas, and contains water. The water adsorbents 10 each having the water absorbing material 8 covered with a resin film 9 dispersed therein.

(Embodiment 2) The foam insulation 4 in Embodiment 2 will be described with reference to FIG.
The closed cell 5 is filled with a volatile foaming agent. Further, inside the closed cells 5, an alkali metal carbonate or an alkaline earth metal carbonate 7 generated by a reaction between an alkali metal hydroxide or an alkali earth metal hydroxide and carbon dioxide gas is applied to the resin film 9. And a water adsorbent 10 in which a water-absorbing substance 8 containing water is covered with a resin film 9.

(Embodiment 3) The foam insulating material 4 in Embodiment 3 will be described with reference to FIG.
The closed cell 5 is filled with a volatile foaming agent. In the closed cells 5, an alkali metal carbonate or an alkaline earth metal carbonate 7 formed by reacting an alkali metal hydroxide or an alkaline earth metal hydroxide with carbon dioxide gas contains water. The substance contained in the moisture adsorbent 10 in which the water absorbing substance 8 thus obtained is covered with the resin film 9 is dispersed.

The alkali metal hydroxide or alkaline earth metal hydroxide of the present invention includes lithium hydroxide, calcium hydroxide, sodium hydroxide, potassium hydroxide,
An alkali metal hydroxide or an alkaline earth metal hydroxide that adsorbs carbon dioxide and generates a carbonate, such as barium hydroxide, can be used. In addition, dehydrating alkali metal or alkaline earth metal hydroxides such as sodium hydroxide,
It is preferable to coat in advance with a resin film.

The water-absorbing substance of the present invention has the same effect as long as it is a compound capable of absorbing and removing moisture, such as silica gel, zeolite, activated carbon, activated alumina, calcium chloride and the like.

The alkali metal hydroxide of the present invention includes
Sodium hydroxide, potassium hydroxide, lime soda, and the like, which absorbs carbon dioxide to generate carbonate and further have a water adsorption ability, can be used.

Examples of the resin film material of the present invention include a film mainly composed of ethyl cellulose and acrylic, a film mainly composed of vinyl acetate, a film mainly composed of urethane, and a film mainly composed of silicone. And, any effect can be obtained as long as it transmits water vapor.

The reactive foaming agent of the present invention is preferably a compound which reacts with isocyanate such as water or lower carboxylic acid to generate carbon dioxide gas.

The volatile foaming agent of the present invention acts as a main foaming agent of the resin composition, and is preferably a compound having good compatibility with the polyol composition and having a small gas thermal conductivity. As specific examples, hydrocarbon compounds such as cyclopentane, n-pentane, isopentane, neopentane, butane, and isobutane are suitable from the viewpoint of global environmental protection. Among them, cyclopentane having a low gas thermal conductivity is applied. Things are more desirable. Similarly, HFC-356 mmf, HFC-245fa and the like, which are hydrofluorocarbon foaming agents, can be applied.

There is no problem even if two or more volatile foaming agents are mixed and applied.

[0061]

Next, specific examples of the present invention will be described.

Example 1 The polyol was a mixture of an aromatic amine-based polyether polyol and an ethylenediamine-based polyether polyol, and had a total hydroxyl value of 460 mg.
The KOH / g foam stabilizer was F-335 manufactured by Shin-Etsu Chemical Co., Ltd., and the catalyst was Kaolyzer No. manufactured by Kao Corporation. 1. Pure water was used as the reactive foaming agent, and cyclopentane was used as the volatile foaming agent. Hydroxide that becomes carbonate after carbon dioxide gas adsorption has an average particle size of 300.
μm lithium hydroxide reagent manufactured by Toyo Chemicals Co., Ltd. Each having a coating having an average film thickness of 2 μm was used. Each of the above-described raw materials was mixed in a predetermined blending number to constitute a premix component.

On the other hand, the isocyanate component is an organic polyisocyanate comprising polymeric MDI having an amine equivalent of 135.

The premix component and the isocyanate component are mixed and stirred by a high-pressure foaming machine, and the first wall member and
The space formed by the second wall member was foam-filled to form a heat insulating box. Cure at 45 ° C for 5 hours.
Minutes.

(Example 2) To a hydroxide that becomes a carbonate after carbon dioxide adsorption, a lithium hydroxide reagent manufactured by Toyo Chemicals having an average particle size of 300 μm was mixed with ethyl cellulose using a centrifugal flow type coating device manufactured by Freund Corporation. A film having an average film thickness of 2 μm was prepared using a resin as a main component, and as a moisture adsorbent, silica gel A type manufactured by Fuji Silysia Chemical Ltd. having an average particle diameter of 200 μm was used in the same apparatus as a resin with ethyl cellulose as a main component. Each having a coating having a thickness of 2 μm was used.

The same premix component and isocyanate component as in Example 1 were used.

The premix component and the isocyanate component are mixed and stirred by a high-pressure foaming machine, and the first wall member and
The space formed by the second wall member was foam-filled to form a heat insulating box. Cure at 45 ° C for 5 hours.
Minutes.

(Example 3) A hydroxide which becomes a carbonate after carbon dioxide gas adsorption is a lithium hydroxide reagent manufactured by Toyo Chemicals having an average particle diameter of 300 μm, and a water adsorbent is Fuji Silysia Chemical having an average particle diameter of 200 μm. Silica gel A type manufactured by the Company was used, and both of them used a centrifugal flow type coating machine manufactured by Freund Corporation to form a coating having an average film thickness of 2 μm with a resin containing ethyl cellulose as a main component.

The same premix component and isocyanate component as in Example 1 were used.

The premix component and the isocyanate component are mixed and stirred by a high-pressure foaming machine, and the first wall member and
The space formed by the second wall member was foam-filled to form a heat insulating box. Cure at 45 ° C for 5 hours.
Minutes.

Example 4 A lithium hydroxide reagent having an average particle diameter of 300 μm manufactured by Toyo Chemicals Co., Ltd. was mixed with a hydroxide that becomes a carbonate after carbon dioxide gas adsorption using ethyl cellulose with a centrifugal flow type coating apparatus manufactured by Freund Corporation. A film having an average film thickness of 2 μm was prepared using a resin as a main component, and as a moisture adsorbent, sodium hydroxide manufactured by Kanto Denka Kogyo Co., Ltd. with an average particle size of 50 μm was used. Each having a coating having an average film thickness of 2 μm was used.

The same premix component and isocyanate component as in Example 1 were used.

The premix component and the isocyanate component are mixed and stirred with a high-pressure foaming machine, and the first wall member and
The space formed by the second wall member was foam-filled to form a heat insulating box. Cure at 45 ° C for 5 hours.
Minutes.

(Example 5) A hydroxide which becomes a carbonate after carbon dioxide gas adsorption is a lithium hydroxide reagent manufactured by Toyo Chemicals having an average particle diameter of 300 μm, and a water adsorbent is Kanto Denka Kogyo Co., Ltd. which has an average particle diameter of 50 μm. Both sodium hydroxides were used, each of which was used to form a coating having an average film thickness of 2 μm with a resin containing an acrylic resin as a main component using a centrifugal flow type coating device manufactured by Freund Corporation.

The same premix component and isocyanate component as in Example 1 were used.

The premix component and the isocyanate component are mixed and stirred by a high-pressure foaming machine, and the first wall member and
The space formed by the second wall member was foam-filled to form a heat insulating box. The curing was performed at 45 ° C. for 5 minutes.

(Example 6) As a moisture adsorbing substance which also serves as a hydroxide which becomes a carbonate after adsorbing carbon dioxide gas, an average particle diameter of 50 μm was used.
m, using a sodium hydroxide manufactured by Kanto Denka Kogyo Co., Ltd., and a coating having an average film thickness of 2 μm was formed with a resin containing acrylic resin as a main component by a centrifugal flow type coating device manufactured by Freund Corporation.

The same premix component and isocyanate component as in Example 1 were used.

The premix component and the isocyanate component are mixed and stirred by a high-pressure foaming machine, and the first wall member and
The space formed by the second wall member was foam-filled to form a heat insulating box. Cure at 45 ° C for 5 hours.
Minutes.

The heat-insulating boxes of Examples 1 to 6 were disassembled, and the initial density of the foam sample, the gas composition in the cells, and the thermal conductivity of the foam 1 day and 7 days after the foaming were measured. In addition, 30 × 40 × 5c prepared with the same prescription
The foam swelling was measured using an m-size panel foam.

The thermal conductivity was 20 × 2 from the heat insulating box.
A foam having a size of 0 × 2.5 cm was cut out and measured with AUTO-Λ manufactured by Eiko Seiki Co., Ltd. The gas composition in the bubbles was measured by gas chromatography manufactured by Shimadzu Corporation.

Table 1 shows the number of components and the evaluation results for Examples 1 to 6. Further, a case where only lithium hydroxide is used as the carbon dioxide adsorbent at the same time (Comparative Example 1) is also shown.

[0083]

[Table 1]

As described above, the foamed heat insulating material of Example 1 of the present invention adsorbs lithium hydroxide as a hydroxide reacting with carbon dioxide and water generated as a by-product due to the reaction with carbon dioxide. By using silica gel as the moisture adsorbent, the gas component inside the closed cells of the foamed heat insulating material is filled with cyclopentane, which is a volatile foaming agent, and the foamed heat insulating material having excellent heat insulating performance, and the heat insulating box body It turned out to be obtained.

Further, since the silica gel is coated with the resin film, it did not absorb the pure water and did not affect the urethane reaction in the process of forming the foamed heat insulating material.

Further, lithium hydroxide does not inhibit the generation of carbon dioxide gas by the reaction between the reactive blowing agent and the polyisocyanate. In addition, since the reaction between lithium hydroxide and carbon dioxide proceeds more slowly than the reaction for generating carbon dioxide, the generated carbon dioxide can contribute to the formation of bubbles in the foamed heat insulating material.

On the other hand, lithium hydroxide reacts with carbon dioxide gas remaining inside the bubbles after the foamed heat insulating material is formed to form a carbonate. Thus, it is considered that the gas component remaining inside the cells was substantially filled with cyclopentane, which is a volatile foaming agent, and the gas thermal conductivity inside the closed cells of the foamed heat insulating material could be improved.

Further, silica gel adsorbs water generated as a by-product by the reaction between lithium hydroxide and carbon dioxide gas. Thus, it is considered that the ratio of the volatile foaming agent in the gas component remaining inside the cells is further increased, and the gas thermal conductivity inside the closed cells of the foamed heat insulating material can be improved.

Further, the foamed heat insulating material of Example 2 of the present invention comprises, as a hydroxide reacting with carbon dioxide, lithium hydroxide previously coated with a resin film, and a reaction between carbon dioxide and hydroxide. By using silica gel coated with a resin film as a water-adsorbing substance that adsorbs water generated as a by-product, the gas component inside the closed cells of the foamed insulating material is filled with a volatile blowing agent cyclopentane, Foam insulation with excellent insulation performance, and
It turned out that an insulated box was obtained.

Further, in Example 2, the swelling amount of the foam was suppressed. This is because the reaction between lithium hydroxide and carbon dioxide gas is delayed by coating the lithium hydroxide with a resin film, and the carbon dioxide gas adsorption reaction proceeds slowly after the foam is cured, thereby suppressing the generation of moisture during the resin curing stage. It is thought that it was possible.

Further, the foamed heat insulating material of Example 3 of the present invention has a structure in which lithium hydroxide is contained in the inside of the moisture adsorbent in which the silica gel is coated with the resin film, and the gas inside the closed cells of the foamed heat insulating material is provided. The components were filled with cyclopentane which is a volatile foaming agent, and it was found that a foamed heat insulating material having excellent heat insulating performance and a heat insulating box were obtained.

Further, in Example 3, it was found that the effect of reducing the thermal conductivity appeared early. This is because, because lithium hydroxide and silica gel are both contained in the resin film, silica gel exists near the reaction site of the carbon dioxide gas adsorption reaction,
It is considered that this is because moisture, which is a factor of heat insulation performance deterioration generated by a side reaction, can be quickly adsorbed and removed.

Further, the foamed heat insulating material of Example 4 of the present invention comprises lithium hydroxide previously coated with a resin film as a hydroxide reacting with carbon dioxide gas, and a reaction between carbon dioxide gas and hydroxide. By using sodium hydroxide coated with a resin film as a moisture-adsorbing substance that adsorbs water generated as a by-product, the gas components inside the closed cells of the foamed heat insulating material are filled with cyclopentane, a volatile foaming agent. Foam insulation with excellent insulation performance,
And it turned out that a heat insulation box is obtained.

Further, in Example 4, the effect of reducing the thermal conductivity was improved. This is because sodium hydroxide used as a moisture adsorbent is capable of adsorbing and removing carbon dioxide gas, so that the amount of lithium hydroxide added can be reduced, and the hygroscopic performance of sodium hydroxide is improved. This is considered to be because the water content can be completely absorbed and removed with a small amount of addition due to the high amount, and the addition amount of the solid component can be reduced.

Further, the foamed heat insulating material of Example 5 of the present invention has a structure in which lithium hydroxide is contained inside the film of the moisture adsorbent in which sodium hydroxide is coated with a resin film.
It was found that the gas component inside the closed cells of the foamed heat insulating material was filled with cyclopentane, which is a volatile foaming agent, so that a foamed heat insulating material having excellent heat insulating performance and a heat insulating box were obtained.

Further, in Example 5, it was found that the effect of reducing the thermal conductivity appeared early. This is because lithium hydroxide and sodium hydroxide are both contained in the resin film, so that sodium hydroxide is present in the vicinity of the reaction site of the carbon dioxide gas adsorption reaction, and is a factor in lowering the heat insulation performance generated by a side reaction. This is presumably because water can be quickly adsorbed and removed.

In the foamed heat insulating material of Example 6 of the present invention, the sodium hydroxide acts as a carbon dioxide gas adsorbent and a moisture adsorbent, so that the gas component inside the closed cells of the foamed heat insulating material is: It was found that a foamed heat insulating material filled with cyclopentane as a volatile foaming agent and having excellent heat insulating performance, and a heat insulating box were obtained.

Further, in Example 6, it can be seen that a reduction in the thermal conductivity appears at an early stage, and that the effect is great. This is because sodium hydroxide acts as both a carbon dioxide adsorbent and a moisture adsorbent, so that the adsorption and removal of moisture after the carbon dioxide adsorption reaction proceeds rapidly, and as a result, sodium hydroxide Can be reduced,
This is considered to be because deterioration of the thermal conductivity due to the addition of the solid component was suppressed.

[0099] In Comparative Example 1, the improvement in thermal conductivity was small even though carbon dioxide gas was removed. This is considered to be because water having high thermal conductivity generated by the side reaction exists inside the bubbles.

As a result, an ozone depletion potential of 0, which is indispensable for protecting the global environment, and cyclopentane, which is one of the hydrocarbons having almost no effect on global warming, is used as a foaming agent for urethane foam to achieve high heat insulation performance. It is possible to provide a high-quality foamed heat insulating material, a method of manufacturing the foamed heat insulating material, and a high-quality heat-insulating box in which the foamed heat-insulating material is foam-filled.

[0101]

As described above, according to the present invention, the carbon dioxide in the foamed heat insulating material is adsorbed and removed, and the moisture generated by the carbon dioxide adsorption reaction does not adversely affect the heat insulating performance. Excellent foam insulation and its manufacturing method,
And an insulated box can be provided.

[Brief description of the drawings]

FIG. 1 is a partially cutaway perspective view of a heat insulating box according to one embodiment of the present invention.

FIG. 2 is a schematic view of a foam insulation according to Embodiment 1 of the present invention.

FIG. 3 is a schematic view of a foam insulation material according to a second embodiment of the present invention.

FIG. 4 is a schematic view of a foam insulation material according to Embodiment 3 of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Insulation box 2 1st wall member 3 2nd wall member 4 Foam insulation material 5 Bubble 6 Bubble wall 7 Alkali metal carbonate or alkaline earth metal carbonate 8 Water absorbing material 9 Resin film 10 Moisture adsorbent

Claims (14)

[Claims] 1. A foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, comprising at least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate and water. A foamed heat insulating material comprising: a water adsorbent in which a water-absorbing substance comprising at least one of an organic or inorganic compound is coated with a resin film. 2. The foamed heat insulating material according to claim 1, wherein the carbonate is coated with a resin film. 3. The water adsorbent in which the carbonate is contained in a resin film coated with a water-absorbing substance comprising at least one of an organic or inorganic compound containing water. Foam insulation. 4. The foamed heat insulating material according to claim 1, wherein the water-absorbing substance is an alkali metal hydroxide. 5. The foamed thermal insulation according to claim 1, wherein at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains. Wood. 6. A polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, and at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide, in addition to a polyisocyanate. And, mixed with a water adsorbent coated with a resin film of a water-absorbing substance comprising at least one of organic or inorganic compounds, foamed, carbon dioxide gas generated by the reaction of water and polyisocyanate inside closed cells, and Forming a foamed polyurethane resin composition containing a volatile foaming agent, wherein the hydroxide adsorbs carbon dioxide in closed cells of the foamed polyurethane resin composition to form carbonate, and substantially forms the closed cells. The step of completely filling with a volatile foaming agent, and the step in which the hydroxide generates water when adsorbing carbon dioxide gas in the closed cells of the foamed polyurethane resin composition, the organic or A step of absorbing water by a moisture adsorbent coated with a resin film with a water-absorbing substance comprising at least one inorganic compound. 7. The method according to claim 6, wherein the hydroxide is previously coated with a resin film. 8. The foamed thermal insulation according to claim 6, wherein the hydroxide is contained in the inside of the moisture adsorbent film in which the resin film is coated with a water-absorbing substance comprising at least one of an organic or inorganic compound. The method of manufacturing the material. 9. The method according to claim 6, wherein the water-absorbing substance is an alkali metal hydroxide. 10. A space formed by a first wall member, a second wall member, the first wall member, and the second wall member is filled with a volatile foaming agent. The foamed polyurethane resin composition having closed cells is filled, and the resin composition contains at least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate and at least one of an organic or inorganic compound containing water. A heat-insulating box, comprising a water-absorbing agent in which a water-absorbing substance comprising a resin film is coated. 11. The heat insulating box according to claim 10, wherein the carbonate is coated with a resin film. 12. The heat-insulating box according to claim 10, wherein the carbonate is contained in the inside of the moisture adsorbent film in which a water-absorbing substance comprising at least one of an organic or inorganic compound is coated with a resin film. . 13. The heat insulating box according to claim 10, wherein the water absorbing material is an alkali metal hydroxide. 14. The heat insulating box according to claim 10, wherein at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains. body.