JPH09302128A - Foamed heat insulting material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foamed heat insulating material capable of improving the thermal conductivity of gas by fixing carbon dioxide in the closed cells of the foamed heat insulating material with an epoxide compound and removing and capable of maintaining heat insulting performances excellent with time. SOLUTION: This foamed heat insulating material 5 comprises a foamed polyurethane resin composition having closed cells of a resin. The resin composition contains at least a urethane bond, a urea bond, a carbonate synthetic catalyst and a carbonate obtained by reacting an epoxide with carbon dioxide. The closed cells contain a volatile blowing agent and a fluorine-based hydrocarbon having a partial pressure lower than that of the volatile blowing 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 used in refrigerators, freezers and the like, and a method for producing the foamed heat insulating material.

[0002]

2. Description of the Related Art In recent years, chlorofluorocarbon (hereinafter referred to as C)
Environmental problems such as ozone layer depletion and global warming due to hydrochlorofluorocarbons (hereinafter referred to as HCFCs) have been attracting attention.
Hydrocarbons (hereinafter referred to as HC
Are referred to) and hydrofluorocarbons (hereinafter referred to as HFCs), and various studies such as the application of volatile foaming agents and the method of using carbon dioxide obtained by the reaction of cyanate and water as a part of the foaming agents have been conducted.

However, cyclopentane, which is a typical HC-based blowing agent, has a higher gas thermal conductivity than CFCF11, which is a conventional general-purpose blowing agent, and is a urethane foam insulating material foamed using these HC-based blowing agents. The foam has poor thermal conductivity. In addition, carbon dioxide obtained by the reaction between isocyanate and water has a higher gas thermal conductivity than that of the HC-based foaming agent. Has the problem of deteriorating the thermal conductivity of the foam.

Therefore, in the past, in improving the heat insulating property of the foamed heat insulating material, efforts have been made to improve the radiant heat conductivity by miniaturizing the bubble diameter, and to reduce the carbon dioxide tissue ratio in the bubble to reduce the gas heat conductivity. Has been done.

For example, as reported in Japanese Patent Application Laid-Open No. 7-12604, carbon dioxide having a high gas thermal conductivity existing in bubbles is immobilized and removed by an epoxide compound, and the heat insulating property of the urethane foam is obtained. There are suggestions to improve. When this technology is used, when volatile organic compounds with low gas thermal conductivity and carbon dioxide generated by the reaction of isocyanate and water are applied as a foaming agent, immediately after foaming, carbon dioxide and volatile in the foam bubbles are generated. Although it is filled with the mixed gas of the vapor of the organic compound, the epoxide compound gradually reacts with carbon dioxide to synthesize the carbonate compound.

Therefore, as the gas component ratio of the volatile organic compound having a low gas thermal conductivity increases with time, the gas thermal conductivity of the mixed gas in the bubbles decreases, and the foam thermal conductivity improves.

Further, in the above-mentioned proposed embodiment, it is preferable that the foamed heat insulating material is suitable for being filled in a hermetically sealed refrigerator box constituted by combining a metallic outer box and a hard resin inner box. Stated.

[0008]

However, as in the above-mentioned proposal, the foamed heat insulating body is filled in a closed refrigerator box constituted by combining a metallic outer box and a hard resin inner box. Even when it is applied, the long-term use of the refrigerator deteriorates the heat insulating property of the refrigerator heat insulating box body due to the influence of the air that enters the air bubbles through the hard resin inner box.

This is because the gas composition ratio of the volatile organic compound is lowered by the invasion of air into the bubbles, and the gas thermal conductivity of the mixed gas in the bubbles is deteriorated.

Particularly, when a volatile organic compound having a low vapor pressure is applied as a foaming agent, the partial pressure of the volatile organic compound in the bubbles becomes small, so that the amount of air invading the bubbles is the same. However, it is expected that the heat insulation performance will be greatly affected. Further, in the reaction-reduced pressure type foam heat insulating material to which the epoxide compound is applied, carbon dioxide, which has a lower gas thermal conductivity than air, hardly exists, so that the influence of air invasion on the heat insulating performance becomes particularly large. Therefore, it has been a problem to suppress the invasion of air into the bubbles of the foamed heat insulating material as much as possible.

Further, the epoxide compound has a high affinity with the urethane raw material, and the bubble diameter becomes larger than that of the conventional non-reactive decompression type foam insulation material containing no epoxide compound.
There was also a problem that the radiant heat conductivity deteriorates.

It is an object of the present invention to provide a foamed heat insulating material which has excellent heat insulating properties and whose deterioration of the foam thermal conductivity of the heat insulating box is small even with time.

It is another object of the present invention to provide a method for producing a foamed heat insulating material which is excellent in heat insulating property and whose deterioration of the foam heat conductivity of the heat insulating box is small with time.

[0014]

The foam insulation material of the present invention is
A foamed polyurethane resin composition having closed cells, wherein the resin composition contains at least a urethane bond, a urea bond, a carbonate synthesis catalyst, and a carbonate compound formed by reacting an epoxide compound and carbon dioxide, and It is characterized in that a volatile foaming agent and a cell-refining agent are contained inside the cells at a partial pressure lower than the partial pressure of the volatile foaming agent. According to the present invention, it is possible to obtain a foamed heat insulating material which is excellent in heat insulating property and whose deterioration of the foam thermal conductivity of the heat insulating box is small even with time.

The foamed heat insulating material of the present invention comprises a foamed polyurethane resin composition having closed cells, and at least a urethane bond, a urea bond, a carbonate synthesis catalyst, an epoxide compound and carbon dioxide react in the resin composition. And a volatile foaming agent inside the closed cells, and a fluorine-containing hydrocarbon compound at a partial pressure lower than the partial pressure of the volatile foaming agent. According to the present invention, it is possible to obtain a foamed heat insulating material which is excellent in heat insulating property and whose deterioration of the foam thermal conductivity of the heat insulating box is small even with time.

The foamed heat insulating material of the present invention is composed of a foamed polyurethane resin composition having closed cells, and at least a urethane bond, a urea bond, a carbonate synthesis catalyst, an epoxide compound and carbon dioxide react in the resin composition. And a volatile blowing agent inside the closed cells, and a fluorinated tertiary amine compound at a partial pressure lower than the partial pressure of the volatile blowing agent. According to the present invention, it is possible to obtain a foamed heat insulating material which has excellent heat insulating properties and whose deterioration of the foam thermal conductivity of the heat insulating box is small even with time.

The foamed heat insulating material of the present invention comprises a foamed polyurethane resin composition having closed cells, and at least a urethane bond, a urea bond, a carbonate synthesis catalyst, an epoxide compound and carbon dioxide react in the resin composition. And a hydrocarbon compound contained in the closed cells at a partial pressure lower than the partial pressure of the volatile foaming agent. According to the present invention, it is possible to obtain a foamed heat insulating material which is excellent in heat insulating property and whose deterioration of the foam thermal conductivity of the heat insulating box is small even with time.

The foamed heat insulating material of the present invention is composed of a foamed polyurethane resin composition having closed cells, and at least a urethane bond, a urea bond, a carbonate synthesis catalyst, an epoxide compound and carbon dioxide react in the resin composition. And a fluorinated surfactant, and a volatile foaming agent inside the closed cells. According to the present invention, it is possible to obtain a foamed heat insulating material which is excellent in heat insulating property and whose deterioration of the foam thermal conductivity of the heat insulating box is small even with time.

The method for producing a foamed heat insulating material of the present invention comprises an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound and a carbonate synthesis catalyst. The method is characterized in that a bubble-refining agent is mixed and stirred to generate foam. According to the present invention, it is possible to provide a method for producing a foamed heat insulating material which is excellent in heat insulating properties and whose deterioration of the foam thermal conductivity of the heat insulating box body is small over time.

The method for producing a foamed heat insulating material of the present invention comprises an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound and a carbonate synthesis catalyst. It is characterized in that a fluorine-based hydrocarbon compound is mixed and stirred to generate foam. According to the present invention, it is possible to provide a method for producing a foamed heat insulating material which is excellent in heat insulating properties and whose deterioration of the foam thermal conductivity of the heat insulating box body is small over time.

The method for producing a foamed heat insulating material of the present invention comprises an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound and a carbonate synthesis catalyst. , A fluorinated tertiary amine compound is mixed and stirred to generate foam. According to the present invention, it is possible to provide a method for producing a foamed heat insulating material which is excellent in heat insulating properties and whose deterioration of the foam thermal conductivity of the heat insulating box body is small over time.

The method for producing a foamed heat insulating material of the present invention comprises an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound and a carbonate synthesis catalyst. , A hydrocarbon compound is mixed and stirred to generate foam.
According to the present invention, it is possible to provide a method for producing a foamed heat insulating material which is excellent in heat insulating properties and whose deterioration of the foam thermal conductivity of the heat insulating box body is small over time.

The method for producing a foamed heat insulating material of the present invention comprises an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound and a carbonate synthesis catalyst. , A fluorine-based surfactant is mixed and stirred to generate foam. According to the present invention, it is possible to provide a method for producing a foamed heat insulating material which is excellent in heat insulating properties and whose deterioration of the foam thermal conductivity of the heat insulating box body is small over time.

The heat insulating box body of the present invention is characterized in that the foamed heat insulating material is filled in the space formed by the face material and the face material to be molded. According to the present invention, it is possible to obtain a heat insulating box which is excellent in heat insulating property and whose deterioration of foam thermal conductivity of the heat insulating box is small with time.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention comprises a foamed polyurethane resin composition having closed cells, wherein at least a urethane bond is contained in the resin composition,
It contains a urea bond, a carbonate synthesis catalyst, a carbonate compound formed by the reaction of an epoxide compound and carbon dioxide, and a volatile foaming agent inside the closed cells, and a fine cell bubble at a partial pressure lower than the partial pressure of the volatile foaming material. A foamed heat insulating material characterized by containing an agent, the thickness of the foam film of the foamed heat insulating agent does not change, and the bubble diameter decreases, so it has excellent heat insulating properties, and even over time It is possible to obtain a foamed heat insulating material with little deterioration in foam thermal conductivity.

Further, the foamed heat insulating material is a premix component prepared by previously mixing a polyol composition, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, and a cell refiner. Further, three components of an epoxide compound solution component prepared by mixing and stirring an epoxide compound, a carbonate synthesis catalyst, and an isocyanate component are mixed and stirred by a high-pressure foaming machine to generate foam.

At this time, since the air bubble refining agent is added to and mixed with the premix component, the surface tension of the premix component is lowered, air is easily entrained in the raw material by stirring, and the entrained air is fragmented. Can be achieved. As a result, the number of foam nuclei that serve as the nuclei for forming bubbles increases, so that the urethane foam insulation can be made finer.

Further, the epoxide compound dispersed in the urethane resin composition undergoes an addition reaction with carbon dioxide in bubbles in the presence of a carbonate synthesis catalyst to form a cyclic carbonate,
Carbon dioxide in bubbles is fixed and removed. Therefore, since the gas composition ratio in the bubbles of the volatile organic compound applied as the volatile foaming agent is increased, the foam thermal conductivity is improved.

However, even if the carbon dioxide in the bubbles is fixed and removed and the internal pressure of the bubbles is reduced, the thickness of the bubble film of the foamed heat insulating material is hardly changed, and the fineness of the bubbles is achieved. The barrier effect is improved due to the shielding effect by the increase in the number of bubbles in the gas diffusion direction corresponding to the increase in the gas diffusion rate, the amount of air invading from the atmosphere into the bubbles with time is reduced, and the deterioration of the heat insulating performance with time can be suppressed.

Further, since the bubble diameter is made fine, the radiation heat conduction is reduced, and thus the foam heat conductivity is improved.
In addition, since the partial pressure inside the bubbles of the cell refiner is lower than the partial pressure of the volatile foaming agent, the foam thermal conductivity is high even when the gas thermal conductivity of the vapor of the cell refiner is high. Has little effect on.

The invention according to claim 2 of the present invention comprises a foamed polyurethane resin composition having closed cells,
The resin composition contains at least a urethane bond, a urea bond, a carbonate synthesis catalyst, a carbonate compound formed by reacting an epoxide compound and carbon dioxide, and a volatile foaming agent inside the closed cells and a volatile foaming agent. It is a foam insulation material characterized in that it contains a fluorine-based hydrocarbon compound at a partial pressure lower than the partial pressure of the foam insulation film. It is possible to obtain a foamed heat insulating material which is excellent and has little deterioration in the foam heat conductivity of the heat insulating box over time.

Further, the foamed heat insulating material is a premix component prepared by previously mixing a polyol composition, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, and a fluorine-containing hydrocarbon compound. , And an epoxide compound, an epoxide mixed solution component prepared by mixing and stirring a carbonate synthesis catalyst, and an isocyanate component are mixed and stirred by a high-pressure foaming machine to generate foam.

At this time, since the fluorine-based hydrocarbon compound is added to and mixed with the premix component, the surface tension of the premix component is lowered, and it is easy to entrain air in the raw material by stirring, and the entrained air is fragmented. Can be achieved. on the other hand,
The fluorine-based hydrocarbon compound is difficult to dissolve in the premix components and is finely divided and dispersed as an emulsion in the premix. As a result, the number of foam nuclei that serve as the nuclei for forming bubbles increases, so that the urethane foam insulation can be made finer.

Further, the epoxide compound dispersed in the urethane resin composition undergoes an addition reaction with carbon dioxide in bubbles in the presence of a carbonate synthesis catalyst to form a cyclic carbonate,
Carbon dioxide in bubbles is fixed and removed. Therefore, since the gas composition ratio in the bubbles of the volatile organic compound applied as the volatile foaming agent is increased, the foam thermal conductivity is improved.

However, even if the carbon dioxide in the bubbles is fixed and removed and the internal pressure of the bubbles is reduced, the thickness of the bubble film of the foamed heat insulating material is hardly changed, and the fineness of the bubbles is achieved. The barrier effect is improved due to the shielding effect by the increase in the number of bubbles in the gas diffusion direction corresponding to the increase in the gas diffusion rate, the amount of air invading from the atmosphere into the bubbles with time is reduced, and the deterioration of the heat insulating performance with time can be suppressed.

Further, since the bubble diameter is made finer, the radiation heat conduction is reduced and the foam heat conductivity is improved.
In addition, since the partial pressure inside the bubbles of the fluorine-based hydrocarbon compound is lower than the partial pressure of the volatile foaming agent, even if a fluorine-based hydrocarbon compound with high gas thermal conductivity is applied, the foam heat The effect on conductivity is small.

The invention according to claim 3 of the present invention comprises a foamed polyurethane resin composition having closed cells,
The resin composition contains at least a urethane bond, a urea bond, a carbonate synthesis catalyst, a carbonate compound formed by reacting an epoxide compound and carbon dioxide, and a volatile foaming agent inside the closed cells and a volatile foaming agent. It is a foamed heat insulating material characterized by containing a fluorine-based tertiary amine compound at a partial pressure lower than the partial pressure of, and the bubble diameter is reduced without changing the thickness of the foamed film of the foamed heat insulating material. It is possible to obtain a foamed heat insulating material which is excellent in heat resistance and whose deterioration of the foam heat conductivity of the heat insulating box is small even with time.

Further, the foamed heat insulating material is a premix prepared by previously mixing a polyol composition, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, and a fluorine-based tertiary amine compound. Three components, an epoxide compound, an epoxide mixed solution component prepared by mixing and stirring a carbonate synthesis catalyst, and an isocyanate component are mixed and stirred by a high-pressure foaming machine to generate foam.

At this time, since the fluorine-based tertiary amine compound is added to and mixed with the premix component, the surface tension of the premix component is lowered, and it is easy to entrain air in the raw material by stirring, and the entrained air is finely divided. Can be realized. On the other hand, the fluorine-based tertiary amine compound is difficult to dissolve in the premix component and is finely divided and dispersed as an emulsion in the premix. As a result, the number of foam nuclei that serve as the nuclei for forming bubbles increases, so that the urethane foam insulation can be made finer.

Further, the epoxide compound dispersed in the urethane resin composition undergoes an addition reaction with carbon dioxide in bubbles in the presence of a carbonate synthesis catalyst to form a cyclic carbonate,
Carbon dioxide in bubbles is fixed and removed. Therefore, since the gas composition ratio in the bubbles of the volatile organic compound applied as the volatile foaming agent is increased, the foam thermal conductivity is improved.

However, even if the carbon dioxide in the bubbles is fixed and removed and the internal pressure of the bubbles is lowered, the thickness of the bubble film of the foamed heat insulating material is hardly changed, and the fineness of the bubbles is achieved. The barrier effect is improved due to the shielding effect by the increase in the number of bubbles in the gas diffusion direction corresponding to the increase in the gas diffusion rate, the amount of air invading from the atmosphere into the bubbles with time is reduced, and the deterioration of the heat insulating performance with time can be suppressed.

Further, since the bubble diameter is made fine, the radiant heat conduction is reduced and the foam heat conductivity is improved. Further, since the partial pressure in the bubbles of the fluorine-based tertiary amine compound is lower than the partial pressure of the volatile foaming agent, the influence on the foam thermal conductivity is small even when the fluorine-based tertiary amine compound having high gas thermal conductivity is applied. .

According to a fourth aspect of the present invention, there is provided a foamed polyurethane resin composition having closed cells,
The resin composition contains at least a urethane bond, a urea bond, a carbonate synthesis catalyst, a carbonate compound formed by reacting an epoxide compound and carbon dioxide, and a volatile foaming agent inside the closed cells and a volatile foaming agent. Is a foam insulation material characterized in that it contains a hydrocarbon compound at a partial pressure lower than the partial pressure of, because the thickness of the foam film of the foam insulation material does not change the bubble diameter is reduced, excellent heat insulation, Moreover, a foamed heat insulating material can be obtained in which deterioration of the foam thermal conductivity of the heat insulating box is small over time.

Further, the foamed heat insulating material is a premix component prepared by previously mixing a polyol composition, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, and a hydrocarbon compound, Further, three components of an epoxide compound solution component prepared by mixing and stirring an epoxide compound and a carbonate synthesis catalyst, and an isocyanate component are mixed and stirred by a high-pressure foaming machine to generate foam.

At this time, since the hydrocarbon compound which is hardly dissolved in the polyol composition is added and mixed to the premix component, the hydrocarbon compound is finely divided and dispersed as an emulsion in the premix. As a result, the number of foam nuclei that serve as the nuclei for forming bubbles increases, so that the urethane foam insulation can be made finer.

Further, the epoxide compound dispersed in the urethane resin composition undergoes an addition reaction with carbon dioxide in bubbles in the presence of a carbonate synthesis catalyst to form a cyclic carbonate,
Carbon dioxide in bubbles is fixed and removed. Therefore, since the gas composition ratio in the bubbles of the volatile organic compound applied as the volatile foaming agent is increased, the foam thermal conductivity is improved.

However, even if the carbon dioxide in the bubbles is fixed and removed and the internal pressure of the bubbles is reduced, the thickness of the bubble film of the foamed heat insulating material is hardly changed, and the fineness of the bubbles is achieved. The barrier effect is improved due to the shielding effect by the increase in the number of bubbles in the gas diffusion direction corresponding to the increase in the gas diffusion rate, the amount of air invading from the atmosphere into the bubbles with time is reduced, and the deterioration of the heat insulating performance with time can be suppressed.

Further, since the bubble diameter is made finer, the radiant heat conduction is reduced and the foam heat conductivity is improved.
In addition, since the partial pressure in the bubbles of the hydrocarbon compound is lower than the partial pressure of the volatile foaming agent, there is no effect on the foam thermal conductivity even when a hydrocarbon compound with high gas thermal conductivity is applied. small.

The invention according to claim 5 of the present invention comprises a foamed polyurethane resin composition having closed cells,
The resin composition contains at least a urethane bond, a urea bond, a carbonate synthesis catalyst, a carbonate compound formed by reacting an epoxide compound and carbon dioxide, and a fluorine-based surfactant, and volatile foaming inside the closed cells. A foamed heat insulating material characterized by containing an agent, the thickness of the foam film of the foamed heat insulating material does not change, and the bubble diameter decreases, so that it has excellent heat insulating properties, and even over time It is possible to obtain a foamed heat insulating material with little deterioration in foam thermal conductivity.

Further, this foamed heat insulating material is a premix component prepared by previously mixing a polyol composition, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, and a fluorine-containing surfactant. , And an epoxide compound and a carbonate synthesis catalyst are mixed and stirred, and three components of an epoxide mixed solution component and an isocyanate component are mixed and stirred by a high-pressure foaming machine to generate foam.

At this time, since the fluorine-based surfactant is added to and mixed with the premix component, the surface tension of the premix component is greatly reduced due to its surface activating action.
Further, since it also has an action of improving the foamability, it is possible to easily entrain air in the raw material by stirring and subdivide the entrained air. As a result, the number of foam nuclei that serve as the nuclei for forming bubbles increases, so that the urethane foam insulation can be made finer.

Further, the epoxide compound dispersed in the urethane resin composition undergoes an addition reaction with carbon dioxide in bubbles in the presence of a carbonate synthesis catalyst to form a cyclic carbonate,
Carbon dioxide in bubbles is fixed and removed. Therefore, the foam gas thermal conductivity is improved because the gas composition ratio in the bubbles of the volatile organic compound applied as the volatile foaming material is increased.

However, even if the carbon dioxide in the bubbles is fixed and removed and the internal pressure of the bubbles is reduced, the thickness of the bubble film of the foamed heat insulating material is hardly changed, and the bubble miniaturization is achieved. The barrier effect is improved due to the shielding effect due to the increase in the number of bubbles in the gas diffusion direction corresponding to the increase in temperature, and the deterioration of the heat insulating performance over time can be suppressed even if the amount of air intrusion from the atmosphere into the bubbles over time is reduced.

Further, since the bubble diameter is made finer, the radiation heat conduction is reduced and the foam heat conductivity is improved.

The invention according to claim 6 of the present invention is an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, and a carbonate synthesis catalyst. And a bubble-refining agent are mixed and stirred to generate foam, which is a method for producing a foamed heat insulating material, in which the bubble diameter is reduced without changing the thickness of the foamed film of the foamed heat insulating material. It is possible to obtain a foamed heat insulating material which is excellent in heat resistance and whose deterioration of the foam heat conductivity of the heat insulating box is small even with time.

The invention according to claim 7 of the present invention is an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, and a carbonate synthesis catalyst. And a fluorine-based hydrocarbon compound are mixed and stirred to generate foam, and a method for producing a foamed heat insulating material, wherein the bubble diameter is reduced without changing the thickness of the foamed film of the foamed heat insulating material. It is possible to obtain a foamed heat insulating agent which has excellent properties and whose deterioration of the foam thermal conductivity of the heat insulating box body is small over time.

The invention according to claim 8 of the present invention is an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, and a carbonate synthesis catalyst. And a fluorine-based tertiary amine compound are mixed and stirred to generate foam, and a method for producing a foamed heat insulating material, wherein the bubble diameter is reduced without changing the thickness of the foamed film of the foamed heat insulating material, It is possible to obtain a foamed heat insulating material which is excellent in heat insulating property and whose deterioration of the foam heat conductivity of the heat insulating box body is small over time.

The invention according to claim 9 of the present invention is an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, and a carbonate synthesis catalyst. And a hydrocarbon compound are mixed and stirred to generate foam, which is a method for producing a foamed heat insulating agent, wherein the bubble diameter is reduced without changing the thickness of the foamed film of the foamed heat insulating material. It is possible to obtain a foamed heat insulating material which is excellent and has little deterioration in the foam heat conductivity of the heat insulating box over time.

The tenth aspect of the present invention provides an isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, and a carbonate synthesis catalyst. And a fluorine-based surfactant are mixed and stirred to generate foam, which is a method for manufacturing a foamed heat insulating material, in which the bubble diameter is reduced without changing the thickness of the foamed film of the foamed heat insulating material. It is possible to obtain a foamed heat insulating material which is excellent in properties and whose deterioration of the foam thermal conductivity of the heat insulating box is small even with time.

According to an eleventh aspect of the present invention, a foamed heat insulating material according to any one of the first to fifth aspects is filled in a face material and a space formed by the face material and molded. A foamed heat insulating material having excellent heat insulating properties and having little deterioration in foam thermal conductivity of the heat insulating box over time can be obtained.

A portable device according to the present invention will be described below with reference to FIGS. 1 and 2. (Embodiment 1) FIG. 1 shows a heat insulating box 1 in which a face material (inner box) 2 which is a vacuum molded body of an ABS resin composition and a face material (outer box) 3 formed by forming a steel plate are flanges. The foamed heat insulating material 5 is filled in the space formed through the space 4.

Further, the foamed heat insulating material 5 will be described with reference to FIG. 2. The urethane bond 6 (Chemical Formula 1) formed by the reaction between the isocyanate and the polyol composition reacts with the isocyanate and water as the reactive foaming agent. Urea bond generated by
(Chemical Formula 2), a carbonate synthesis catalyst 8, a carbonate compound 9 (Chemical Formula 3) formed by an addition reaction of an epoxide compound and carbon dioxide, a volatile foaming agent 10, and a volatile foaming agent having a lower partial pressure. It is composed of a high pressure fluorine-containing hydrocarbon compound 11.

[0063]

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[0064]

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[0065]

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(Embodiment 2) The method for producing the foamed heat insulating material 5 of FIG. 1 is as follows: a polyol composition, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, and a fluorine-based compound. The hydrocarbon compounds are premixed to form premix component A. In addition, an epoxide mixed solution component B is prepared by mixing and stirring an epoxide compound and a carbonate synthesis catalyst.

Thereafter, the three components of the premix component A, the epoxide mixed solution component B and the isocyanate component C are mixed and stirred using a high pressure foaming machine to generate foam.

The constituent materials of the present invention will be described in detail below. The cell-refining agent of the present invention is a compound having an action of reducing the cell diameter of closed cells constituting a foamed heat insulating material, and contains at least a fluorine-based hydrocarbon compound, a fluorine-based tertiary amine compound, and a hydrocarbon compound. , Or a fluorine-based sea surface active agent can be applied. It is more preferable that the cell-refining agent is a compound having low compatibility with the polyol composition and low compatibility with the volatile foaming agent. Furthermore, when the amount of the cell-refining agent added is 1/10 or less of the number of moles of the volatilizing agent added, or the partial pressure of the cell-refining agent in the cells is 1/10 or less of the partial pressure of the volatile foaming agent. That is, it is more desirable because the volatile foaming agent has a small influence on the gas thermal conductivity and the storage stability of the premix raw material is good.

The fluorine-containing hydrocarbon compound of the present invention has a carbon number, a linear, branched or cyclic molecular structure, and the number of fluorine substitutions to the hydrocarbon compound, but it has a boiling point near room temperature, It is effective that the compound itself has low surface tension and poor compatibility with the polyol composition. Particularly, a highly fluorinated hydrocarbon compound is preferable. Further, there is no particular problem even with an alkene having an unsaturated group.

As specific examples, perfluoropentane, perfluorohexane, perfluoroheptane, and perfluorooctane, which are fully fluorinated hydrocarbons having 5 to 8 carbon atoms, are particularly effective. As the volatile foaming agent, a combination with a hydrocarbon-based foaming agent having poor compatibility with a fluorine-based hydrocarbon compound has a particularly large effect of making bubbles fine.

Further, even if a small amount of them contributes to bubble miniaturization, the degree of influence is small even when a compound having a high global warming potential is applied. Moreover, when a high boiling point compound is applied, the degree of influence thereof is further reduced.

The fluorine-containing tertiary amine compound of the present invention has a carbon number, a linear, branched or cyclic molecular structure, and the number of fluorine substitutions of the tertiary amine compound, but it has a boiling point near room temperature. It is effective that the compound itself has a low surface tension and poor compatibility with the polyol composition. Particularly, highly fluorinated tertiary amine compounds are preferable. As specific examples, perfluoromethylmorpholine and perfluoroethylmorpholine are particularly effective. As the volatile foaming agent, a combination with a hydrocarbon-based foaming agent having poor compatibility with a fluorine-based tertiary amine compound has a particularly large effect of reducing the bubble diameter.

Similarly, a small amount of these contributes to bubble miniaturization, and when a compound having a high global warming potential is applied, its influence degree becomes extremely small. Moreover, when a high boiling point compound is applied, the degree of influence thereof is further reduced. Furthermore,
Since the fluorine-based tertiary amine compound has a fire extinguishing effect, it has the effect of making the foamed heat insulating material flame-retardant, in addition to the effect of making the cells finer when using other bubble finer agents. It is particularly effective to apply it to a foam insulation material to which a volatile foaming agent is applied.

The hydrocarbon compound of the present invention is not particularly limited in terms of carbon number, linear, branched or cyclic molecular structure,
Those having a linear structure are effective because they have poor compatibility with the polyol composition. As specific examples, hexane, heptane, octane, nonane, decane, undecane, and dodecane are desirable. Further, as the volatile foaming agent, a combination with an HFC-based foaming agent having poor compatibility with a hydrocarbon compound has a particularly large effect of reducing the bubble diameter.

Since pentane having a carbon number of 5 has a relatively good compatibility with the polyol composition, it has a small effect of refining the bubble diameter. Further, hydrocarbons having 4 or less carbon atoms are not suitable because they have a low boiling point and a high risk of explosion.

The fluorosurfactant of the present invention is one in which the hydrogen atoms of the alkyl group of the hydrocarbon surfactant are all replaced by fluorine atoms, and the structure of the amphiphilic group is not particularly limited, and it is anionic. It works effectively in any of cationic, amphoteric and nonionic forms. As specific examples, perfluoroalkyl sulfonates, perfluorocarboxylic acid salts, perfluoroalkyl trimethyl ammonium salts, perfluoroalkyl amino sulfonates, perfluoroalkyl phosphoric acid esters and the like can be applied. In addition,
As the volatile foaming agent, a combination with a hydrocarbon-based foaming agent having poor compatibility with a fluorine-based sea surface active agent has a particularly large effect of reducing the bubble diameter.

The effect of making bubbles finer is obtained by applying at least one of the above-mentioned fluorine type hydrocarbon compounds, fluorine type tertiary amine compounds, hydrocarbon compounds and fluorine type surfactants. Although they can be obtained, of course, there is no particular problem even if these are mixed and applied. As a result, the fineness of the bubbles is achieved with almost no change in the thickness of the foam film of the foamed heat insulating material, so that the number of bubbles in the gas diffusion direction corresponding to the miniaturization of the bubble diameter is increased. The barrier property of itself is improved, the permeation rate of gas in bubbles into the atmosphere,
In addition, the invasion speed of air in the air into the bubbles is reduced, and deterioration of the heat insulating performance over time can be controlled. Further, improvement of foam heat insulation performance due to reduction of radiation heat conduction can be expected.

Any compound having an epoxy group or a glycidyl group can be used as the epoxide compound of the present invention. 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.
Furthermore, when an epoxide compound having a boiling point near room temperature is applied, it acts as a foaming agent for the urethane resin composition and can also be applied as a volatile foaming agent. As specific examples, ethylene oxide, propylene oxide, 1,2-butylene oxide, cis 2,3-butylene oxide, trans 2,3-
Butylene oxide, isobutylene oxide, glycidyl methyl ether, glycidyl ethyl ether, glycidyl butyl ether, glycidyl phenyl ether and the like can be used.

As the carbonate synthesis catalyst of the present invention,
The compounds having nucleophilicity and electrophilicity can be applied alone or in combination. In addition, preferably, as the nucleophile,
A halogen ion is effective, and a compound in which the halogen ion is a counter ion of an onium salt or an alkali halide is particularly preferable. Further, as the electrophile, Lewis acidic metal halide, organic tin halide, organic tin fatty acid ester and the like are preferable.

As a specific example, the nucleophile is particularly preferably a halogenated tetraalkylammonium salt or a halogenated tetraalkylphosphonium salt, and the alkyl group is not particularly limited.

As the alkali halide, chlorides such as lithium, sodium and potassium, bromides and iodides can be applied.

As the electrophile, zinc halides such as zinc chloride, zinc bromide, zinc iodide, and dibutyltin dilaurate are particularly desirable.

By applying the above catalyst, carbon dioxide and an epoxide compound undergo an addition reaction with time in a urethane foam to synthesize a liquid or solid cyclic carbonate composition. When present, the reaction easily proceeds under normal pressure and normal temperature.

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.

The volatile foaming agent of the present invention acts as the main foaming agent of the urethane resin composition, has a relatively high vapor pressure at room temperature, has good compatibility with the polyol composition, and is a gas. A compound having a low thermal conductivity is desirable. As specific examples, cyclopentane, n-pentane, isopentane, neopentane, butane, hydrocarbon compounds such as isobutane are suitable from the viewpoint of global environmental protection, and among them, cyclopentane having a low gas thermal conductivity is more desirable. . Similarly, HFC-356mmf, which is a hydrofluorocarbon-based foaming agent, and HFC
-245fa or the like can be applied. There is no problem even if two or more volatile foaming agents are mixed and applied.

Further, a fluorine-based hydrocarbon compound, a fluorine-based tertiary amine compound, or a hydrocarbon compound, which is a bubble-refining agent applied for the purpose of reducing the bubble diameter of the foamed heat insulating agent, may be a compound having a boiling point near room temperature. When applied, it acts as a foaming agent like a volatile foaming agent. However, in reality, the addition amount is extremely small, and their partial pressure in the bubbles of the foam insulation is small compared to the partial pressure of the volatile foaming agent, so the effect on foam foaming efficiency and gas thermal conductivity is affected. Is small. Furthermore, when the fluorine-based hydrocarbon compound or the fluorine-based tertiary amine compound or the hydrocarbon compound of the bubble refiner is a compound having a high boiling point,
The effects on foam foaming efficiency and gas thermal conductivity are almost negligible. More desirably, the amount of the bubble refiner added is
One-tenth or less of the number of moles added of the volatile foaming agent, or the partial pressure of the cell-refining agent in the bubbles is 10 times the partial pressure of the volatile foaming agent.
When it is 1 / or less, it is favorable from the viewpoint of the influence on the gas thermal conductivity of the mixed gas in the bubbles and the storage stability of the premix raw material.

Isocyanates, polyols, foam stabilizers, urethane polymerization catalysts and the like which constitute the foamed heat insulating material of the present invention are particularly problematic in general-purpose raw materials applied to general hard and soft urethane foamed heat insulating materials. Can be used without. In addition, more preferably, the isocyanate is crude MDI and the polyol is a hydroxyl value of 400 to 550 mg KO.
Good application of H / g tolylenediamine-based polyether polyols. As the foam stabilizer, a silicone-based foam stabilizer is suitable for miniaturizing bubbles, but a fluorine-based foam stabilizer can also be applied.

Next, a specific example of the present invention will be described. (Example 1) Isocyanate is crude MDI having an amine equivalent of 135, and polyol is GR manufactured by Takeda Pharmaceutical Co., Ltd.
Hydroxyl number is 465 mgKOH / g with 46 tolylenediamine-based polyether polyol, F-337 made by Shin-Etsu Chemical Co., Ltd. which is a silicone-based surfactant as a foam stabilizer, Kaolyzer NO1 made by Kao Corporation as a urethane polymerization catalyst, The reactive foaming agent is pure water, the volatile foaming agent is cyclopentane, the epoxide compound is 1,2-epoxide butane, the carbonate synthesis catalyst is a mixture of tetranormalbutylammonium bromide and zinc chloride, and the fluorine-containing hydrocarbon compound is n-.
PF-5060 manufactured by Sumitomo 3M Limited was used as perfluoronormal hexane, which is a complete fluoride of hexane.

With respect to the above compounds, a component A obtained by mixing a polyol, a foam stabilizer, a kaolizer NO1, cyclopentane, pure, and perfluoro normal hexane, 1,2-epoxybutane, and tetranormal butyl ammonium bromide. , Component B mixed with zinc chloride,
Three components C, which consisted of isocyanate, were mixed and stirred in a high-pressure foaming machine, and the space formed of a face material made of iron and a face material made of ABS was foam-filled to form a heat insulating box. In addition, the isocyanate equivalent ratio was set to 1.1 with respect to the component A, and the urethane reactivity was set to be GT 50 seconds. The curing was performed at 45 ° C. for 8 minutes.

Example 2 Isocyanate was crude MDI having an amine equivalent of 135, polyol was GR46 tolylenediamine polyether polyol of GR46 manufactured by Takeda Pharmaceutical Co., Ltd., hydroxyl value was 465 mgKOH / g, and foam stabilizer was silicone surface. Shin-Etsu Chemical Co., Ltd. F-3 which is an activator
37, urethane polymerization catalyst is Kaolyzer NO1 manufactured by Kao Corporation, reactive blowing agent is pure water, volatile blowing agent is cyclopentane, epoxide compound is 1,2-epoxybutane,
As the carbonate synthesis catalyst, PF-5052 manufactured by Sumitomo 3M Limited was used, which was a mixture of tetra-normal butyl ammonium bromide and zinc chloride, and perfluoromethylmorpholine which was a fluorine-based complete fluoride.

Component A prepared by mixing the above compound with a polyol, a foam stabilizer, a kaolizer NO1, cyclopentane, pure and perfluoromethylmorpholine.
Component B obtained by mixing 1,2-epoxybutane, tetranormal butyl ammonium bromide and zinc chloride
And three components C, which consisted of isocyanate, were mixed and stirred in a high-pressure foaming machine, and foamed and filled in a space portion composed of a face material made of iron and a face material made of ABS to form a heat insulating box. In addition, the isocyanate equivalent ratio was set to 1.1 with respect to the component A, and the urethane reactivity was set to be GT 50 seconds. The curing was performed at 45 ° C. for 8 minutes.

Example 3 Isocyanate was crude MDI having an amine equivalent of 135, polyol was a tolylenediamine type polyether polyol of GR46 manufactured by Takeda Pharmaceutical Co., Ltd., hydroxyl value was 465 mgKOH / g, and foam stabilizer was a silicone type sea level. Shin-Etsu Chemical Co., Ltd. F-3 which is an activator
37, urethane polymerization catalyst is Kaolyzer No. 1 manufactured by Kao Corporation. The reactive foaming agent is pure water, the volatile foaming agent is cyclopentane, the epoxide compound is 1,2-epoxybutane,
The carbonate synthesis catalyst used was a mixture of tetranormal butyl ammonium bromide and zinc chloride, and the hydrocarbon compound used was n-heptane as a reagent.

With respect to the above compounds, a component A obtained by mixing a polyol, a foam stabilizer, a kaolizer NO1, cyclopentane, pure and n-heptane, 1,2-epoxybutane, and tetra-n-butylammonium bromide. , Component B mixed with zinc chloride and component C composed of isocyanate are mixed and stirred in a high-pressure foaming machine,
A heat insulating box was formed by foam-filling a space formed of an iron face material and an ABS face material.

The isocyanate equivalent ratio was 1.1 with respect to the component A, and the urethane reactivity was set to GT 50 seconds. The curing was performed at 45 ° C. for 8 minutes.

Example 4 Isocyanate was crude MDI having an amine equivalent of 135, polyol was a tolylenediamine-based polyether polyol of GR46 manufactured by Takeda Pharmaceutical Co., Ltd., hydroxyl value was 465 mgKOH / g, and foam stabilizer was a silicone-based sea surface. Shin-Etsu Chemical Co., Ltd. F-3 which is an activator
37, urethane polymerization catalyst is Kaolyzer No. 1 manufactured by Kao Corporation. The reactive foaming agent is pure water, the volatile foaming agent is cyclopentane, the epoxide compound is 1,2-epoxybutane,
The carbonate synthesis catalyst was a mixture of tetra-n-butylammonium bromide and zinc chloride, the fluorine-based surfactant was a perfluoroalkyl carboxylate, and Megafac F-120 manufactured by Dainippon Ink and Chemicals, Inc. was used.

With respect to the above compound, a component A obtained by mixing a polyol, a foam stabilizer, a kaolizer NO1, cyclopentane, pure and Megafac F-120, 1,
3-epoxybutane, tetra-normal butyl ammonium bromide, zinc chloride mixed component B and isocyanate component C are mixed and stirred in a high-pressure foaming machine to produce an iron-made surface material and an ABS-made surface material. The space consisting of and was foam-filled to form a heat-insulating box. In addition, the isocyanate equivalent ratio was set to 1.1 with respect to the component A, and the urethane reactivity was set to be GT 50 seconds. The curing was performed at 45 ° C. for 8 minutes.

The heat insulating box pairs of Examples 1 to 4 prepared by the above method were left at room temperature for one week, and then the heat insulating box pairs were disassembled to prepare foam samples of 300 × 300 × 50 mm size. Leave at ℃. After one month, the air content of the foam sample, the foam thermal conductivity, and the bubble diameter were measured.

The analysis was conducted by further measuring 200 × 200 × 25 mm from the core of the aged foam sample.
Cut out the size of the foam and make it AU made by Eiko Seiki Co., Ltd.
The foam thermal conductivity was measured with TOΛ, and then the sample was finely pulverized in vacuum to collect the diffusing gas and the amount of air was measured. The bubble diameter was analyzed based on an electron micrograph of the foam cross section of the heat transfer surface of the heat insulating box.

Table 1 shows the number of blended parts and the evaluation results for Examples 1 to 4. At the same time, as a comparative example, a case was shown in which none of the bubble-refining agents of the fluorine-based hydrocarbon compound, the fluorine-based tertiary amine compound, the hydrocarbon compound, and the fluorine-based surfactant was added and mixed.

As can be seen from Table 1, any one or more of the above-mentioned fluorine-based hydrocarbon compounds, fluorine-based tertiary amine compounds, hydrocarbon compounds, and fluorine-based surfactants can be used as a cell-refining agent. In the foamed heat insulating material formed by adding and mixing the above, the bubble diameter is made finer and the amount of air invading due to aging is smaller than that of the conventional product shown in the comparative example. Further, the deterioration of the foam thermal conductivity (Kf) is small.

[0101]

[Table 1]

[0102]

As described above, according to the present invention, the foam heat insulation performance is improved due to the reduction of the radiant heat conductivity due to the miniaturization of bubbles in the foam insulation material, and the barrier property of the foam insulation material is improved by the miniaturization of cells. Since the amount of air entering the foamed heat insulating material is reduced, it is possible to obtain an advantageous effect that a foamed heat insulating material is obtained in which deterioration of the foam heat insulating performance of the heat insulating box is small over time.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a heat insulating box according to an embodiment of the present invention.

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

[Explanation of symbols]

 1 Thermal Insulation Box 2 Face Material (Inner Box) 3 Face Material (Outer Box) 4 Flange 5 Foam Insulation Material 6 Urethane Bond 7 Urea Bond 8 Carbonate Synthesis Catalyst 9 Carbonate Compound 10 Volatile Foaming Agent 11 Fluorine Hydrocarbon Compound

Front Page Continuation (72) Inventor Tsukasa Takushima, 4-5-5 Takaidahondori, Higashi-Osaka City, Osaka Prefecture Matsushita Refrigerator Co., Ltd. (72) Masaaki Suzuki, 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd. (72) Inventor Takayoshi Ueno 1006 Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Takashi Hashida, 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.

Claims (11)

[Claims] 1. A carbonate compound composed of a foamed polyurethane resin composition having closed cells, wherein at least a urethane bond, a urea bond, a carbonate synthesis catalyst, and an epoxide compound and carbon dioxide react with each other in the resin composition. A foamed heat insulating material, characterized in that, in addition to being contained, the closed cell contains a volatile foaming agent and a cell-refining agent at a partial pressure lower than the partial pressure of the volatile foaming agent. 2. A carbonate compound comprising a foamed polyurethane resin composition having closed cells, wherein at least a urethane bond, a urea bond, a carbonate synthesis catalyst, and an epoxide compound and carbon dioxide react with each other in the resin composition. In addition to being contained, a foamed heat insulating material characterized in that it contains a volatile foaming agent inside the closed cells and a fluorine-based hydrocarbon compound at a partial pressure lower than the partial pressure of the volatile foaming agent. 3. A carbonate compound composed of a foamed polyurethane resin composition having closed cells, wherein the resin composition contains at least a urethane bond, a urea bond, a carbonate synthesis catalyst, and a carbonate compound obtained by reacting an epoxide compound and carbon dioxide. In addition to being contained, a foamed heat insulating material characterized in that it contains a volatile foaming agent inside the closed cells and a fluorine-based tertiary amine compound at a partial pressure lower than the partial pressure of the volatile foaming agent. 4. A carbonate compound comprising a foamed polyurethane resin composition having closed cells, wherein at least a urethane bond, a urea bond, a carbonate synthesis catalyst, and a epoxide compound and carbon dioxide react with each other in the resin composition. A foamed heat insulating material comprising a volatile foaming agent inside a closed cell and a hydrocarbon compound at a partial pressure lower than the partial pressure of the volatile foaming agent. 5. A foamed polyurethane resin composition having closed cells, at least a urethane bond, a urea bond, a carbonate synthesis catalyst, and a carbonate compound obtained by reacting an epoxide compound and carbon dioxide in the resin composition. A foamed heat insulating material comprising a fluorinated surfactant and a volatile foaming agent inside the closed cells. 6. An isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, a carbonate synthesis catalyst, and a cell refiner are mixed and stirred. A method for producing a foamed heat insulating material, which comprises foaming by foaming. 7. An isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, a carbonate synthesis catalyst, and a fluorine-based hydrocarbon compound are mixed and stirred. A method for producing a foamed heat insulating material, characterized in that the foamed material is produced by foaming. 8. An isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, a carbonate synthesis catalyst, and a fluorine-based tertiary amine compound are mixed. A method for producing a foamed heat insulating material, which comprises foaming by stirring. 9. An isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, a carbonate synthesis catalyst, and a hydrocarbon compound are mixed and stirred. A method for producing a foamed heat insulating material, which comprises foaming. 10. An isocyanate, a polyol, a foam stabilizer, a urethane polymerization catalyst, a reactive foaming agent, a volatile foaming agent, an epoxide compound, a carbonate synthesis catalyst, and a fluorine-based surfactant are mixed and stirred. A method for producing a foamed heat insulating material, characterized in that the foamed material is produced by foaming. 11. A heat-insulating box body, comprising: a face material and a space formed by the face material, filled with the foamed heat-insulating material according to claim 1.