JPH09302124A - Foamed heat insulting material, its production and heat insulating box body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject heat insulting material capable of rapidly adsorbing and removing a carbon dioxide gas in closed cells in a short time and fixing water generated by a side reaction by a reaction, comprising a foamed polyurethane resin composition having closed cells charged with a volatile blowing agent. SOLUTION: This foamed polyurethane resin composition comprises a foamed polyurethane resin composition having closed cells charged with a volatile blowing agent. The resin composition contains a urethane bond, a urea bond, at least one carbonate of an alkaline (earth) carbonate obtained by reacting an alkaline (earth) metal hydroxide with a carbon dioxide and a compound obtained by reacting an epoxy compound with water. A polyol, a foam stabilizer, a catalyst, a reactive blowing agent, a volatile blowing agent and a polyisocyanate are mixed with the alkaline (earth) metal hydroxide and the epoxy compound, expanded and passed through a step, in which the polyurethane resin composition containing a carbon dioxide gas generated by the reaction between the reactive blowing agent and a polyisocyanate and the volatile blowing agent in the closed cells is formed, to give the objective heat insulating material.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, from the viewpoint of energy saving, there is a need to reduce the thermal conductivity of foamed heat insulating materials and improve the heat insulating properties, and at the same time, chlorofluorocarbon (hereinafter referred to as CF
C), further depletion of the ozone layer by hydrochlorofluorocarbon (hereinafter referred to as HCFC), and
Environmental problems such as global warming are drawing attention, and solving them is an extremely important theme.

Therefore, in manufacturing a rigid urethane foam, which is a typical foam insulation material, CFC and
For the purpose of reducing the amount of HCFC used, there are various foaming methods using hydrocarbons (hereinafter referred to as HC), which have no effect on ozone layer depletion and have little effect on global warming (HFC). Efforts are being considered.

Basically, in order to improve the heat insulation performance of the rigid urethane foam, it is important to reduce the gas thermal conductivity of the gas component in the closed closed cells. It has been an effective means to remove carbon dioxide having high conductivity and fill it with a volatile foaming 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 was essential to use carbon dioxide gas generated by the reaction with the isocyanate as the blowing agent component.

However, in such a structure, since the carbon dioxide gas having a large gas thermal conductivity remains in the closed cells of the foamed heat insulating agent, the heat insulation performance of the foamed heat insulating material becomes poor. As an approach to solving such a problem, for example, a method of removing a carbon dioxide gas component with a carbon dioxide gas adsorbent has been proposed as disclosed in Japanese Patent Laid-Open No. 6-322166.

That is, an adsorbent consisting of an alkali metal hydroxide or the like having an excellent carbon dioxide adsorbing performance is previously added and mixed into the raw material, and the produced carbon dioxide is adsorbed and removed by the adsorbent to foam the inside of the closed cells. It is characterized by improving the heat insulation performance by filling with the agent gas.

[0008]

However, in the structure used in Japanese Patent Laid-Open No. 6-322166, the adsorbent composed of an alkali metal hydroxide or the like has the following formula in the reaction process of adsorbing carbon dioxide gas. Water is produced as a side reaction product as shown in Chemical formula 2).

[0009]

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 substantially the inside of the closed cells is a volatile foaming agent having a low thermal conductivity. Although it is possible to increase the ratio of water, at the same time, water produced as a by-product diffuses into the closed bubbles until a constant 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.

Therefore, the carbon dioxide gas in the closed cells of the foamed heat insulating material is adsorbed and removed by the adsorbent made of alkali metal hydroxide or the like, and the water generated as a side reaction does not affect the thermal conductivity. There was a problem to obtain a foamed heat insulating material having a heat insulating performance and a heat insulating box.

In view of the above problems, the present invention rapidly adsorbs and removes carbon dioxide gas in the closed cells of the foamed heat insulating material, and
It is an object of the present invention to provide a foamed heat insulating material having excellent heat insulating performance by immobilizing water generated as a side reaction, and a method for producing the foamed heat insulating material.

In addition, by rapidly adsorbing and removing carbon dioxide gas in the closed cells of the foamed heat insulating material, and by filling the foamed heat insulating material that reacts and immobilizes water generated as a side reaction, the heat insulating material having excellent heat insulating performance is obtained. The purpose is to provide a box.

[0014]

The foam insulation material of the present invention is
It is composed of a foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, and at least a urethane bond, a urea bond, and an alkali metal hydroxide or an alkaline earth metal hydroxide are carbonic acid in the resin composition. At least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate formed by reaction with gas; and a compound having a structural formula (Chemical Formula 1) formed by reacting an epoxy compound with water. It is a feature.

Further, it is characterized in that the carbonate is coated with a resin film. Further, it is characterized in that at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains.

According to the present invention, the gas component inside the closed cells of the foamed heat insulating material is filled with the volatile foaming agent, and the vapor pressure of carbon dioxide having a large gas thermal conductivity and water is extremely low.
A foamed heat insulating material having excellent heat insulating performance can be obtained.

The method for producing a foamed heat insulating material of the present invention is
Polyol, foam stabilizer, catalyst, reactive foaming agent, volatile foaming agent, polyisocyanate, at least one hydroxide of alkali metal hydroxide or alkaline earth metal hydroxide, epoxy A step of forming a foamed polyurethane resin composition containing a carbon dioxide gas generated by a reaction of a reactive foaming agent and a polyisocyanate inside a closed cell, and foaming by mixing with a compound; The oxide adsorbs carbon dioxide gas in closed cells of the foamed polyurethane resin composition to form a carbonate, and the inside of the closed cells is substantially filled with a volatile foaming agent; and the hydroxide is carbon dioxide gas. And the epoxy group of the epoxy compound reacts with water generated at the same time to react with the above compound to produce a compound having the structural formula (Formula 1).

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 previously coated with a resin film together with at least one inorganic or organic compound containing water.

Further, the epoxy compound is characterized in that it is a polyglycidyl ether.

Further, the epoxy compound is a polyglycidyl amine.

Further, the epoxy compound is characterized in that it is a glycerol ether.

Further, the epoxy compound is characterized in that it is an alkylene oxide.

Further, it is 0.9 to the hydroxyl group in the raw material.
It is characterized in that 1.1 equivalents of polyisocyanate having NCO groups are added.

Further, the epoxy compound is treated as a component other than at least the polyol, the catalyst, the reactive foaming agent and the polyisocyanate until the step of mixing the constituent raw materials and foaming.

According to the present invention, the gas component inside the closed cells of the foamed heat insulating material is filled with the volatile foaming agent, and the vapor pressure of carbon dioxide having a large gas thermal conductivity and water is extremely low.
A method for producing a foamed heat insulating material having excellent heat insulating performance can be provided.

Further, the heat insulation box body of the present invention comprises a first wall member, a second wall member, a space formed by the first wall member and the second wall member, A foamed polyurethane resin composition having closed cells filled with a volatile foaming agent is filled, and at least a urethane bond, a urea bond, and an alkali metal hydroxide or an alkaline earth metal hydroxide are carbonated in the resin composition. At least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate formed by reaction with gas; and a compound having a structural formula (Chemical Formula 1) formed by reacting an epoxy compound with water. It is a feature.

Further, it is characterized in that the carbonate is coated with a resin film. Further, it is characterized in that at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains.

According to the present invention, the gas component inside the closed cells of the foamed heat insulating material filled in the heat insulating box is filled with the volatile foaming agent, and carbon dioxide gas having a large gas thermal conductivity and water vapor. It is possible to obtain a heat insulating box having an extremely low pressure and excellent heat insulating performance.

[0030]

BEST MODE FOR CARRYING OUT THE INVENTION The foamed heat insulating material according to claim 1 of the present invention comprises a foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, and at least urethane is contained in the resin composition. A bond, a urea bond, at least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate formed by the reaction of an alkali metal hydroxide or an alkaline earth metal hydroxide with carbon dioxide, and an epoxy compound. And a compound having a structural formula (Chemical formula 1) formed by reacting with water, wherein the gas component inside the closed cells of the foam insulation is filled with a volatile foaming agent, It is possible to obtain a foamed heat insulating material having excellent heat insulating performance, which has extremely low vapor pressure of carbon dioxide and water having high conductivity.

With the above-mentioned constitution, the alkali metal hydroxide or alkaline earth metal hydroxide added as a raw material, and the epoxy compound have a low activity with respect to the reactive foaming agent, and the reactivity of the reactive foaming agent with the polyisocyanate is low. It does not hinder the generation of carbon dioxide gas by the reaction. In addition, the reaction between the alkali metal hydroxide or alkaline earth metal hydroxide and carbon dioxide proceeds more slowly than the carbon dioxide generation reaction, so the generated carbon dioxide contributes to the formation of closed cells in the foam insulation. It becomes possible to do.

On the other hand, the alkali metal hydroxide or alkaline earth metal hydroxide promptly reacts with carbon dioxide gas remaining inside the closed cells after the foamed heat insulating material is formed to form a carbonate. This allows the gas components remaining inside the closed cells to be substantially filled with the volatile blowing agent.

Further, the epoxy compound is activated as a catalyst added for the purpose of synthesizing the polyurethane resin composition, and is generated as a side reaction product by the reaction between the alkali metal hydroxide or alkaline earth metal hydroxide and carbon dioxide gas. Reacts rapidly with water to produce a compound having the structural formula (Formula 1). As a result, the ratio of the volatile foaming agent in the gas component remaining inside the closed cells is further increased, and the gas thermal conductivity inside the closed cells of the foamed heat insulating material can be improved.

Further, a second aspect of the present invention is characterized in that the carbonate is coated with a resin coating, and the gas component inside the closed cells of the foamed heat insulating material is a volatile foaming agent. It is possible to obtain a foamed heat insulating material having excellent heat insulating performance, which is filled with carbon dioxide having a high gas thermal conductivity and extremely low vapor pressure of water.

With the above structure, the alkali metal hydroxide or alkaline earth metal hydroxide coated with the resin coating added as a raw material has low activity with respect to the reactive foaming agent and the reactive foaming agent and the polyisocyanate. It does not inhibit the generation of carbon dioxide gas due to the reaction with. Further, the reaction of the alkali metal hydroxide or alkaline earth metal hydroxide coated with the resin film and carbon dioxide proceeds more slowly than the carbon dioxide generating reaction, so the generated carbon dioxide is
It is possible to contribute to the formation of closed cells in the foamed heat insulating material.

The alkali metal hydroxide or alkaline earth metal hydroxide coated with the resin coating was completely isolated from the other constituent raw materials in a short time until the raw materials were mixed and foaming started. In this state, water added in advance to promote the reaction with carbon dioxide gas is not eluted outside the coating film, and there is no adverse effect such as affecting the urethane reaction activity.

Further, claim 3 of the present invention is characterized in that at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains, which is a foam insulation material. The gas component inside the closed cells is filled with a volatile foaming agent, and a foamed heat insulating material having excellent heat insulating performance in which carbon dioxide gas having a high gas thermal conductivity and water vapor pressure is extremely low can be obtained.

With the above structure, the remaining at least one hydroxide of alkali metal hydroxide or alkaline earth metal hydroxide can also adsorb and remove carbon dioxide gas generated from unreacted isocyanate. Therefore, it is possible to maintain excellent heat insulating performance even with time.

The method for producing a foamed heat insulating material according to claim 4 of the present invention comprises: a polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, a polyisocyanate, and an alkali metal. At least one hydroxide of a hydroxide or alkaline earth metal hydroxide and an epoxy compound are mixed to foam, and carbon dioxide gas generated by the reaction of the reactive foaming agent and polyisocyanate inside the closed cells, A step of forming a foamed polyurethane resin composition containing a volatile foaming agent, the hydroxide adsorbs carbon dioxide gas in the closed cells of the foamed polyurethane resin composition to form a carbonate, When the step of substantially filling with a volatile blowing agent and the epoxy group of the epoxy compound react with water generated at the same time when the hydroxide reacts with carbon dioxide gas, the structural formula of The gas component inside the closed cells of the foamed heat insulating material is filled with a volatile foaming agent, and the vapor pressure of carbon dioxide having a large gas thermal conductivity and the vapor pressure of water is extremely high. A foamed insulation with low and excellent insulation performance is obtained.

The method for producing a foamed heat insulating material according to claim 5 of the present invention is characterized in that the hydroxide is coated with a resin film in advance. The gas component is filled with a volatile foaming agent, and carbon dioxide gas having a high gas thermal conductivity and a vapor pressure of water are extremely low, and a foamed heat insulating material having excellent heat insulating performance can be obtained.

The method for producing a foamed heat insulating material according to claim 6 of the present invention is characterized in that the hydroxide is previously coated with a resin film together with at least one inorganic or organic compound containing water. The gas component inside the closed cells of the foam insulation is filled with a volatile foaming agent, carbon dioxide having a high gas thermal conductivity, and the foam having excellent heat insulation performance with a very low vapor pressure of water. Insulation is obtained.

With the above structure, since the inorganic or organic compound containing water is previously coated with the resin coating, the contained water does not elute to the outside of the coating in the process of forming the foamed heat insulating material, and the urethane is not generated. It does not affect the reaction. Further, it becomes possible to supply the water necessary for the reaction of the hydroxide of alkali metal or the hydroxide of alkaline earth metal with carbon dioxide, and it is possible to promote the reduction of carbon dioxide inside the closed cells. It is a thing.

The method for producing a foam heat insulating material according to claim 7 of the present invention is characterized in that the epoxy compound is a polyglycidyl ether, and the gas component inside the closed cells of the foam heat insulating material is It is possible to obtain a foamed heat insulating material which is filled with a volatile foaming agent, has a high gas thermal conductivity, and has an extremely low vapor pressure of water and which has excellent heat insulating performance.

With the above structure, the epoxy compound composed of polyglycidyl ethers is a part of the resin component constituting the foam film or skeleton by the epoxy ring-opening reaction catalyzed by the raw material component in the process of forming the foamed heat insulating material. Since a crosslinked structure is formed as described above, it is possible to form a hybrid structure of urethane resin and epoxy resin and improve the mechanical strength of the foamed heat insulating material.

The method for producing a foam heat insulating material according to claim 8 of the present invention is characterized in that the epoxy compound is a polyglycidyl amine, and the gas component inside the closed cells of the foam heat insulating material is It is possible to obtain a foamed heat insulating material which is filled with a volatile foaming agent, has a high gas thermal conductivity, and has an extremely low vapor pressure of water and which has excellent heat insulating performance.

With the above structure, the epoxy compound composed of polyglycidyl amines is a part of the resin component forming the foam film or skeleton by the epoxy ring-opening reaction catalyzed by the raw material component in the process of forming the foamed heat insulating material. Since a crosslinked structure is formed as described above, it is possible to form a hybrid structure of urethane resin and epoxy resin and improve the mechanical strength of the foamed heat insulating material. Further, since it has a strong reaction activity by itself in the reaction with water, it becomes possible to rapidly react with water to form a compound having the structure of (Formula 1).

The method for producing a foam heat insulating material according to claim 9 of the present invention is characterized in that the epoxy compound is a glycerol ether, and the gas component inside the closed cells of the foam heat insulating material is It is possible to obtain a foamed heat insulating material which is filled with a volatile foaming agent, has a high gas thermal conductivity, and has an extremely low vapor pressure of water and excellent heat insulating performance.

With the above structure, the epoxy compound composed of glycerol ethers has a crosslinked structure as a part of the resin component constituting the foam film or skeleton by the reaction between the hydroxyl group of the epoxy compound and the polyisocyanate in the process of forming the foamed heat insulating material. Therefore, it is possible to form a hybrid structure of urethane resin and epoxy resin to improve the mechanical strength of the foamed heat insulating material.

The method for producing a foam heat insulating material according to claim 10 of the present invention is characterized in that the epoxy compound is an alkylene oxide, and the gas component inside the closed cells of the foam heat insulating material is It is possible to obtain a foamed heat insulating material which is filled with a volatile foaming agent, has a high gas thermal conductivity, and has an extremely low vapor pressure of water and excellent heat insulating performance.

The method for producing a foamed heat insulating material according to claim 11 of the present invention is characterized by adding 0.9 to 1.1 equivalents of polyisocyanate having an NCO group to the hydroxyl group in the raw material. The gas component inside the closed cells of the foam insulation is filled with a volatile foaming agent, carbon dioxide having a high gas thermal conductivity, and the foam having excellent heat insulation performance with a very low vapor pressure of water. Insulation is obtained.

With the above-mentioned constitution, most of the polyisocyanate having 0.9 to 1.1 equivalents of NCO groups to the hydroxyl group in the raw material reacts with the hydroxyl group component in the raw material, and the reaction with the epoxy compound is extremely high. Less. As a result, it becomes possible to leave sufficient and sufficient epoxy compound for the reaction with the generated water.

According to the twelfth aspect of the present invention, in the method for producing a foamed heat insulating material, at least the polyol, the catalyst, the reactive foaming agent and the polyisocyanate are provided until the epoxy compound is mixed with the constituent raw materials and foamed. The gas component inside the closed cells of the foamed heat insulating material is filled with a volatile foaming agent, and carbon dioxide gas having a large gas thermal conductivity and water vapor pressure are treated as separate components. A foamed insulation having extremely low and excellent insulation performance is obtained.

With the above structure, the epoxy compound does not consume the epoxy group due to the reaction with other constituent raw materials and the polymerization reaction of itself until the step of mixing and foaming the constituent raw materials. As a result, it becomes possible to leave sufficient and sufficient epoxy compound for the reaction with the generated water.

The heat-insulating box according to claim 13 of the present invention is
A first wall member, a second wall member, the first wall member,
And, in the space formed by the second wall member,
A foamed polyurethane resin composition having closed cells filled with a volatile foaming agent is filled, and at least a urethane bond, a urea bond, and an alkali metal hydroxide or an alkaline earth metal hydroxide are carbonated in the resin composition. At least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate formed by reaction with gas; and a compound having a structural formula (Chemical Formula 1) formed by reacting an epoxy compound with water. The gas component inside the closed cells of the foam insulation material filled in the heat insulation box is filled with a volatile foaming agent, and the vapor pressure of carbon dioxide gas with a large gas thermal conductivity and the vapor pressure of water are An insulating box body having extremely low and excellent insulating performance can be obtained.

The heat insulating box according to claim 14 of the present invention is
It is characterized in that the carbonate is coated with a resin film, and the gas component inside the closed cells of the foam insulation material filled in the heat insulation box is filled with the volatile foaming agent, and the gas heat conduction is conducted. It is possible to obtain a heat insulating box body having excellent heat insulating performance, in which the vapor pressure of carbon dioxide gas having a high rate and water is extremely low.

The heat insulating box according to claim 15 of the present invention is
It is characterized in that at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains, and the gas component inside the closed cells of the foam insulation filled in the insulation box. Is a carbon dioxide gas having a high gas thermal conductivity and an extremely low vapor pressure of water, and a heat insulating box that maintains excellent heat insulating performance over time can be obtained.

Embodiments of the present invention will be described below with reference to FIGS. 1 and 2. (Embodiment 1) FIG. 1 is a perspective view in which a heat insulating box in one embodiment of the present invention is partially cut away.
Indicates a heat insulating box, and a space formed by the first wall member 2 which is a vacuum forming body of the ABS resin composition and the second wall member 3 formed by processing the steel plate is filled with the polyurethane resin composition. The foamed heat insulating agent 4 is filled and buried.

FIG. 2 is a schematic view of a foamed heat insulating material in one embodiment of the present invention. In the figure, 4 indicates a foamed heat insulating material, and urethane produced mainly by reacting an isocyanate and a polyol composition. Independent of the resin skeleton 5 consisting of a bond, a urea bond formed by a reaction between isocyanate and water as a reactive blowing agent, and a compound having a structural formula (Chemical Formula 1) formed by reacting an epoxy compound with water. At least one of alkali metal carbonate or alkaline earth metal carbonate formed by the reaction of alkali metal hydroxide or alkaline earth metal hydroxide with carbon dioxide is formed inside the closed cell 6. Carbonate 7 is dispersed and filled with a volatile foaming agent.

(Embodiment 2) The method for manufacturing the foamed heat insulating material 4 of FIG. 1 is as follows: a polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, and an alkali metal hydroxide. Alternatively, at least one hydroxide of alkaline earth metal hydroxide is mixed in advance to obtain the premix component A.

Then, the premix component A, the component B consisting of an epoxide compound, and the component C consisting of an isocyanate are mixed and stirred using a high-pressure foaming machine to produce foam.

The constituent materials of the present invention will be described in detail below. Examples of the alkali metal hydroxides or alkaline earth metal hydroxides of the present invention include calcium hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, etc., which adsorb carbon dioxide gas and form carbonates. Any alkali metal or alkaline earth metal hydroxide can be used without any problem. Further, it is preferable that a deliquescent alkali metal or alkaline earth metal hydroxide such as sodium hydroxide is previously coated with a resin film. In addition, hydroxides of alkali metals or alkaline earth metals that require sufficient water to react with carbon dioxide such as calcium hydroxide should be coated with a resin coating together with an inorganic or organic compound containing water in advance. Is preferred.

The water-containing inorganic or organic compound of the present invention has an inorganic hydrate such as magnesium chloride hydrate, barium hydroxide hydrate or sodium carbonate hydrate, or has efflorescence. It is preferable to use an inorganic hydrate capable of dissociating water at room temperature, such as sodium sulfite hydrate, magnesium sulfate hydrate, dibasic sodium phosphate hydrate and zinc sulfate hydrate. Further, an organic compound having excellent water absorption such as an ion exchange resin or a super absorbent resin can also be used.

Further, as the resin film of the present invention, an ethyl cellulose film, a film containing acrylic as a main component, a film containing vinyl acetate as a main component, a film containing urethane as a main component, a film containing silicone as a main component, and the like. The same effect can be obtained as long as it is a resin film through which carbon dioxide gas can pass.

As the epoxide compound of the present invention, any compound having an epoxy group can be applied. The epoxide compound may be monofunctional or polyfunctional. It is also possible to use compounds having an unsaturated group in the molecule, oligomers having epoxy groups at both ends, oxetane and oxetane derivatives. Further, the epoxide compound may be in any form of gas, liquid and solid.

As a specific example, monoglycidyl ethers such as ethyl glycidyl ether, butyl glycidyl ether and phenyl glycidyl ether can be used.

From the viewpoint of improving the strength of the foamed heat insulating material,
Preferred are polyglycidyl ethers such as neopentyl glycol glycidyl ether, ethylene glycol diglycidyl ether, and various epoxy resins represented by polycondensed organisms of bis-phenol A and epichlorohydrin.

As the glycidyl amines, grade 604 manufactured by Yuka Shell Epoxy Co., Ltd. represented by polyglycidyl amine type epoxy resin, Sumitomo Chemical Co., Ltd.
Commercially available grade ELM-120 and the like have a strong reaction activity with water and can be promptly removed by reaction.

As the glycerol ethers,
Glycidol, glycerol polyglycidyl ether and the like.

As the alkylene oxides,
Examples include ethylene oxide, propylene oxide, and 1,2-butylene oxide.

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

The volatile foaming agent of the present invention acts as the main foaming agent of the resin composition, and is a compound having a good compatibility with the polyol composition and a small gas thermal conductivity. desirable. 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.

[0073]

EXAMPLES Hereinafter, the foamed heat insulating material of the present invention will be described with reference to examples.

Example 1 A polyol has a hydroxyl value of 46.
5 mgKOH / g tolylenediamine-based polyether polyol, the foam stabilizer is a silicone-based surfactant, Shin-Etsu Chemical Co., Ltd. F-337, the catalyst is dimethylcyclohexylamine, and Kao (shares). ) Kaolizer No. 10 is water as a reactive foaming agent, cyclopentane is a volatile foaming agent, and a hydroxide which becomes a carbonate after carbon dioxide is adsorbed is a lithium hydroxide reagent manufactured by Toyo Chemicals Co., Ltd. having an average particle diameter of 300 μm. used. The above ingredients are mixed in a predetermined blending number, and a premix component A
It was constituted as.

As the epoxy compound of the component B, phenyl glycidyl ether manufactured by NOF CORPORATION was used.

As the isocyanate component of the component C, crude MDI having an amine equivalent of 135 was used.

Premix components prepared and mixed in this way
Component B consisting of A and epoxy compound, and isocyanate
The component C consisting of
Foaming with foaming machine, composed of first wall member and second wall member
The filled space was filled to obtain a heat insulating box. In addition, foam break
Regarding the packing density of the heat material, the average density of the core part is 38 kg / m. ^Three
It was adjusted so that

Example 2 Wako Pure Chemical Industries, Ltd. having an average particle size of 50 μm as a hydroxide which becomes a carbonate after adsorption of carbon dioxide
A heat-insulating box was obtained in the same manner as in Example 1 except that a sodium hydroxide reagent manufactured by the company was used and that the resin was previously coated with a resin film.

The resin film was prepared by using a centrifugal fluidized coating granulator manufactured by Freund Sangyo Co., Ltd. to granulate a resin having ethyl cellulose as a main component as a binder, and further, using the same device, a film having an average film thickness of 2 μm was formed. It was created.

Example 3 Katayama Chemical Co., Ltd. having an average particle size of 50 μm was used as a hydroxide which becomes a carbonate after carbon dioxide is adsorbed.
A calcium hydroxide reagent manufactured by Wako Pure Chemical Industries, Ltd., which was previously coated with a resin coating together with a sodium sulfite heptahydrate reagent manufactured by Wako Pure Chemical Industries, Ltd. was used, and other raw materials were heat-insulated in the same manner as in Example 1. I got a box.

The resin coating was prepared in the same manner as in Example 2. (Example 4) As the epoxy compound of the component B, polybisidyl ethers such as bis-phenol A type epoxy resin EP-4300 manufactured by Asahi Denka Co., Ltd. were used, and the other raw materials were the same as in Example 1. I got a heat insulation box.

Example 5 As the epoxy compound of the component B, polyglycidylamines 630 manufactured by Yuka Shell Epoxy Co., Ltd. was used. Obtained.

(Example 6) As the epoxy compound of component B, glycerol diglycidyl ether G-100 manufactured by NOF CORPORATION, which is a glycerol ether, was used.
Other materials were obtained in the same manner as in Example 1 to obtain a heat-insulated box.

Example 7 As the epoxy compound of the component B, 1,2-epoxybutane reagent manufactured by Wako Pure Chemical Industries, Ltd., which is an alkylene oxide, was used.
A heat insulating box was obtained in the same manner as in Example 1.

The hard urethane foam of the heat-insulating box thus obtained was cut out, and the thermal conductivity after 1 and 7 days of foaming, the gas composition in the bubbles, and the compressive strength in the heat transfer direction were measured. The measurement results are shown in (Table 1). The thermal conductivity is AUTO-Λ manufactured by Hidehiro Seiki Co., Ltd., the gas composition in the bubbles is gas chromatography manufactured by Shimadzu Corporation, and the compression strength is manufactured by Shimadzu Corporation. It was measured by an autograph.

At the same time, as a comparative example, when no epoxy compound was added and only lithium hydroxide was added as a hydroxide (Comparative Example A), sodium hydroxide was previously added as a hydroxide without adding an epoxy compound. When a resin coated with ethyl cellulose as a main component is used (Comparative Example B), the epoxy compound is not added and calcium hydroxide as a hydroxide is coated with sodium sulfite heptahydrate in a resin coating. In the case of using (Comparative Example C) and using the same raw material as in Example 1 and adding an isocyanate having an NCO group of 0.89 equivalent to the hydroxyl group in the raw material (Comparative Example D), The case where 1.11 equivalents of isocyanate having an NCO group was added (Comparative Example E) is also shown in (Table 1).

[0087]

[Table 1]

As described above, in the foamed heat insulating material of Example 1 of the present invention, lithium hydroxide is generated as a hydroxide that reacts with carbon dioxide gas, and as a by-product by the reaction of carbon dioxide gas and hydroxide. By using phenylgylcidyl ether as an epoxy compound that reacts with water, the gas component inside the closed cells of the foam insulation is filled with cyclopentane, which is a volatile foaming agent, and the foam insulation having excellent heat insulation performance, It was also found that a heat-insulating box can be obtained.

This is because lithium hydroxide added as a hydroxide that reacts with carbon dioxide reacts rapidly with carbon dioxide remaining inside the closed cells after the foamed heat insulating material is formed to form lithium carbonate. . As a result, the gas component remaining inside the closed cells can be substantially filled with the volatile blowing agent cyclopentane.

Further, phenyl glycidyl ether, which is an epoxy compound, receives the activity of a catalyst composed of dimethylcyclohexylamine added for the purpose of synthesizing a polyurethane resin composition, and reacts with lithium hydroxide and carbon dioxide gas to produce a side reaction product. Reacts rapidly with the water generated as phenyl diglycerol ether. It is considered that the ratio of the volatile blowing agent cyclopentane in the gas component remaining inside the closed cells was further increased by this, and the gas thermal conductivity inside the closed cells of the foamed heat insulating material was improved.

Further, the foamed heat insulating material of Example 2 in the present invention was prepared by reacting carbon dioxide gas with hydroxide which was previously coated with a resin film as hydroxide which reacts with carbon dioxide, and by reacting carbon dioxide with hydroxide. By using phenyl glycidyl ether as an epoxy compound that reacts with water generated as a by-product, the gas component inside the closed cells of the foam insulation is filled with cyclopentane, which is a volatile foaming agent, and has excellent heat insulation performance. It was found that the foamed heat insulating material and the heat insulating box having the same can be obtained.

It is considered that this is due to the same effect as that of the first embodiment. In addition, sodium hydroxide having deliquescent,
Since it is coated with a resin coating in advance, it does not adsorb water outside the resin coating and is completely isolated from other constituent raw materials in the short time when it is added to the premix components and the raw materials are mixed and foaming starts. It existed in the above-mentioned state and did not affect the urethane activity.

The foamed heat insulating material of Example 3 of the present invention was prepared by using calcium hydroxide as a hydroxide which reacts with carbon dioxide gas and coating it with a resin coating together with sodium sulfite heptahydrate. In addition, by using phenylglycidyl ether as an epoxy compound that reacts with water generated as a by-product by the reaction of carbon dioxide gas and hydroxide, the gas component inside the closed cells of the foam insulation is volatile foaming agent. Is filled with cyclopentane,
It was found that a foamed heat insulating material having excellent heat insulating performance and a heat insulating box can be obtained.

It is considered that this is due to the same effect as that of the first embodiment. In addition, since calcium hydroxide, which requires sufficient water for the reaction with carbon dioxide, is previously coated with a resin coating together with sodium sulfite heptahydrate, it is possible to quickly fix carbon dioxide. And again,
It is added to the premix components without elution of water to the outside of the resin coating, and in the short time when the raw materials are mixed and foaming starts, it exists in a state completely isolated from other constituent raw materials, and affects the urethane reaction. I didn't give it.

In the foamed heat insulating material of Example 4 of the present invention, lithium hydroxide is generated as a hydroxide which reacts with carbon dioxide gas, and is also generated as a by-product by the reaction of carbon dioxide gas and hydroxide. By using a bis-phenol A type epoxy resin that is a polyglycidyl ether as the epoxy compound that reacts with water, the gas component inside the closed cells of the foamed heat insulating material is filled with cyclopentane that is a volatile foaming agent, Foam insulation with excellent insulation performance,
And it turned out that a heat insulation box is obtained.

It is considered that this is due to the same effect as that of the first embodiment. Further, by using a bis-phenol A type epoxy resin which is a polyglycidyl ether, it is possible to improve the compressive strength of the foamed heat insulating material, and there is no deformation of the heat insulation box due to shrinkage deformation of the foamed heat insulating material over time. An excellent heat insulating box was obtained.

This is a resin that constitutes a foam film or skeleton by an epoxy ring-opening reaction in which a bis-phenol A type epoxy resin which is a polyglycidyl ether is catalyzed by a raw material component in the process of producing a foamed heat insulating material. Since the crosslinked structure is formed as a part of the components, it is considered that a hybrid structure of urethane resin and epoxy resin is formed to improve the mechanical strength of the foamed heat insulating material.

The foamed heat insulating material of Example 5 of the present invention is lithium hydroxide as a hydroxide which reacts with carbon dioxide gas, and water generated as a by-product by the reaction of carbon dioxide gas and hydroxide. As an epoxy compound that reacts with
By using polyglycidyl amines, the gas component inside the closed cells of the foam insulation is filled with cyclopentane, which is a volatile foaming agent, and the foam insulation having excellent heat insulation performance and the heat insulation box are obtained. I found out that

This has the same effect as in the first embodiment,
Since polyglycidyl amines have strong reaction activity by themselves in the reaction with water, it is considered that they react with water promptly.

Further, by using polyglycidyl amines, it is possible to improve the compressive strength of the foam insulation material, and to obtain an excellent insulation box body which does not deform due to shrinkage deformation of the foam insulation material over time. Was obtained.

It is considered that this is due to the same effect as in the fourth embodiment. Further, the foamed heat insulating material of Example 6 in the present invention reacts with lithium hydroxide as a hydroxide that reacts with carbon dioxide, and with water that is generated as a by-product due to the reaction between carbon dioxide and hydroxide. By using glycerol diglycidyl ether, which is a glycerol ether, as the epoxy compound, the gas component inside the closed cells of the foam insulation is filled with cyclopentane, which is a volatile foaming agent, and it has excellent heat insulation performance. It was found that a material and a heat insulating box can be obtained.

It is considered that this is due to the same effect as that of the first embodiment. In addition, by using polyglycidyl amines, the compressive strength of the foam insulation material can be improved, and an excellent insulation box body that does not deform due to shrinkage deformation of the foam insulation material over time was obtained. .

This is considered to be due to the same effect as in the fourth embodiment. In addition, the foamed heat insulating material of Example 7 of the present invention reacts with lithium hydroxide as a hydroxide that reacts with carbon dioxide, and with water that is generated as a by-product due to the reaction between carbon dioxide and hydroxide. By using 1,2-epoxybutane, which is an alkylene oxide, as the epoxy compound, the gas component inside the closed cells of the foamed heat insulating material is filled with cyclopentane, which is a volatile foaming agent, and has excellent heat insulating performance. It was found that a foamed heat insulating material and a heat insulating box can be obtained.

This is the same effect as in the first embodiment,
It is considered that 1,2-epoxybutane, which is an alkylene oxide, rapidly reacts with water because it has a strong reaction activity in the reaction with water.

Further, 1, which is an alkylene oxide,
By using 2-epoxybutane, the compressive strength of the foam insulation material was improved, and an excellent insulation box body was obtained in which the insulation box body was not deformed due to shrinkage deformation of the foam insulation material over time.

It is considered that this is due to the same effect as in the fourth embodiment. In Comparative Example, when no epoxy compound was added and only lithium hydroxide was added as the hydroxide (Comparative Example 1), the epoxy compound was not added and sodium hydroxide was used as the hydroxide mainly containing ethyl cellulose in advance. When a resin coated as a component is used (Comparative Example 2), and when an epoxy compound is not added and calcium hydroxide as a hydroxide is coated with a resin coating together with sodium sulfite heptahydrate. When used (Comparative Example 3), carbon dioxide gas inside the closed cells could be adsorbed and removed, but water could not be reduced, and the thermal conductivity of the obtained foamed heat insulating material could be sufficiently reduced. could not.

In addition, when the same raw material as in Example 1 was used and 0.89 equivalent of isocyanate having an NCO group was added to the hydroxyl group in the raw material (Comparative Example 3), the obtained foamed heat insulating material was obtained. As a result, the compressive strength of was weak and the external quality of the heat insulation box was significantly impaired.

Further, when the same raw material as in Example 1 was used and 1.11 equivalents of isocyanate having an NCO group was added to the hydroxyl group in the raw material (Comparative Example 4), carbon dioxide gas inside the closed cells was changed. Was able to be adsorbed and removed, but water could not be reduced, and the thermal conductivity of the obtained foamed heat insulating material could not be sufficiently reduced. This is because the epoxy compound phenyl glycidyl ether reacts with the NCO group of the remaining isocyanate before reacting with the water generated by the reaction of lithium hydroxide and carbon dioxide gas,
I think that it is because it was consumed.

[0109]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, the hydroxide that reacts with carbon dioxide reacts rapidly with the carbon dioxide remaining inside the closed cells after the foamed heat insulating material is formed to form a carbonate. By doing so, the gas component remaining inside the closed cells is substantially filled with a volatile foaming agent, and the epoxy compound receives the activity of the catalyst added for the purpose of synthesizing the polyurethane resin composition to form a hydroxide. By reacting with carbon dioxide gas rapidly with water generated as a by-product, the ratio of the volatile blowing agent cyclopentane in the gas component remaining inside the closed cells is further increased, and the foam insulation becomes independent. It is possible to provide a foamed heat insulating material having improved heat conductivity of gas inside bubbles and having excellent heat insulating performance, a method for manufacturing the same, and a heat insulating box.

[Brief description of drawings]

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

FIG. 2 is a schematic view of a foam insulation material according to one embodiment of the present invention.

[Explanation of symbols]

 1 Foam Insulation Material 2 First Wall Member 3 Second Wall Member 4 Foam Insulation Material 5 Resin Skeleton 6 Closed Cell 7 Carbonate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tsukasa Takushima 4-2-5 Takaidahondori, Higashi-Osaka City, Osaka Prefecture Matsushita Refrigerator Co., Ltd. No. 2-5 Matsushita Cold Machinery Co., Ltd.

Claims (15)

[Claims] 1. A foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, wherein at least a urethane bond and a urea bond are contained in the resin composition.
At least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate formed by reacting an alkali metal hydroxide or an alkaline earth metal hydroxide with carbon dioxide, and an epoxy compound reacting with water ( And a compound having the structural formula of Chemical formula 1). Embedded image 2. The foamed heat insulating material according to claim 1, wherein the carbonate is coated with a resin film. 3. The foamed heat insulating material according to claim 1 or 2, wherein at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains. 4. A polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, and a polyisocyanate,
At least one hydroxide of an alkali metal hydroxide or alkaline earth metal hydroxide and an epoxy compound are mixed to foam, and carbon dioxide generated by the reaction between the reactive foaming agent and polyisocyanate inside the closed cells. Forming a foamed polyurethane resin composition containing a gas and a volatile foaming agent, wherein the hydroxide adsorbs carbon dioxide gas in the closed cells of the foamed polyurethane resin composition to form a carbonate, The step of substantially filling the inside of the bubbles with a volatile foaming agent and the water simultaneously generated when the hydroxide reacts with carbon dioxide reacts with the epoxy group of the epoxy compound, and has a structural formula (Formula 1). A method for producing a foam insulation material, the method including the step of producing a compound. 5. The method for producing a foamed heat insulating material according to claim 4, wherein the hydroxide is previously coated with a resin film. 6. The method for producing a foamed heat insulating agent according to claim 4, wherein the hydroxide is previously coated with a resin film together with at least one inorganic or organic compound containing water. 7. The method for producing a foamed heat insulating material according to claim 4, wherein the epoxy compound is a polyglycidyl ether. 8. The method for producing a foamed heat insulating material according to claim 4, wherein the epoxy compound is a polyglycidyl amine. 9. The method for producing a foamed heat insulating material according to claim 4, wherein the epoxy compound is a glycerol ether. 10. The method for producing a foamed heat insulating material according to any one of claims 4 to 6, wherein the epoxy compound is an alkylene oxide. 11. The hydroxyl group in the raw material is 0.9 to 1.
7. A polyisocyanate having 1 equivalent of NCO groups is added, according to any one of claims 4 to 6.
A method for producing a foamed heat insulating material according to item. 12. The epoxy compound is at least a polyol until the step of mixing and foaming the constituent raw materials,
7. The catalyst, the reactive blowing agent, and the polyisocyanate are treated as separate components, and the treatment is performed according to claims 4 to 6.
The method for producing a foamed heat insulating agent according to any one of 1. 13. A space formed by the first wall member, the second wall member, the first wall member and the second wall member is filled with a volatile foaming agent. A polyurethane foam resin composition having closed cells is filled, and at least a urethane bond and a urea bond are contained in the resin composition,
At least one carbonate of an alkali metal carbonate or an alkaline earth metal carbonate formed by reacting an alkali metal hydroxide or an alkaline earth metal hydroxide with carbon dioxide, and an epoxy compound reacting with water And a compound having a structural formula of (Chemical Formula 1). 14. The foamed heat insulating material according to claim 12, wherein the carbonate is coated with a resin film. 15. The heat insulating box according to claim 12, wherein at least one hydroxide of an alkali metal hydroxide or an alkaline earth metal hydroxide remains.