JPH10265606A - Foamed heat insulation material, its production and heat insulation box - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a foamed heat insulation material having excellent heat insulation performances by adding a carbonate synthesis catalyst coated with a resin film and a carbonate compound prepared by reacting an epoxide compound with carbon dioxide to a resin composition having closed cells filled with a volatile blowing agent and containing at least urethane bonds and urea bonds. SOLUTION: The volatile blowing agent used is exemplified by cyclopentane. The carbonate synthesis catalyst used is one prepared by previously coating a powder of a nucleophilic compound (e.g. tetraalkylammonium halide) with a resin film (e.g. ethyl cellulose film). The epoxide compound used has a viscosity of 1,000 Pa.s or below at 25 deg.C and is exemplified by ethyl glycidyl ether. A heat insulation material 4 comprises a resin skeleton 5 comprising urethane bonds, urea bonds and a carbonate compound and closed cells containing a synthesis catalyst 7.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In recent years, from the viewpoint of energy saving, there has been a need to reduce the thermal conductivity of a foamed heat insulating material and improve the heat insulating property.
C), and ozone depletion by hydrochlorofluorocarbon (hereinafter referred to as HCFC), and
Environmental problems such as global warming are attracting attention, and solving them is an extremely important theme. Therefore, in the production of rigid urethane foam, which is a typical foamed heat insulating material, there is no influence on ozone layer destruction for the purpose of reducing the use of CFC and HCFC, and hydrofluorocarbon (hereinafter, HFC) and earth Various approaches are being studied for foaming with hydrocarbons (hereinafter referred to as HC) that have little effect on global warming.

[0003] Basically, in order to improve the heat insulation performance of rigid urethane foam, it is important to reduce the gas thermal conductivity of the gas components in the foam closed cells. Efficient means have been to remove carbon dioxide with high conductivity and fill it with a volatile blowing agent. On the other hand, a reactive blowing agent such as water and an organic polyisocyanate are used for the purpose of reducing the amount of the volatile blowing agent used, the problem of compatibility between the blowing agent and the raw material components, and improving various physical properties of the foam. It was essential to use carbon dioxide generated by the reaction as a foaming agent component.

However, in such a configuration, since the carbon dioxide gas having a large gas thermal conductivity remains in the closed cells of the foamed heat insulating material, the heat insulating performance of the foamed heat insulating material deteriorates. For example, Japanese Patent Application Laid-Open No.
According to Japanese Patent No. 2604, an epoxide compound and an addition reaction catalyst, which is a carbonate-forming catalyst, are added to and contained in a foaming stock solution in advance, and after a foamed heat insulating material is formed, carbon dioxide in closed cells is subjected to an addition reaction with the epoxide compound. This is characterized in that a cyclic carbonate is generated, the partial pressure of carbon dioxide inside the closed cells of the foamed heat insulating material is reduced, and the gas thermal conductivity is improved.

[0005]

However, according to the structure used in Japanese Patent Application Laid-Open No. Hei 7-12604, at the stage of injection foaming, water and polyisocyanate, and polyol and polyisocyanate are equilibrated as a main reaction. The addition reaction catalyst between the epoxide compound and carbon dioxide is
Since it has the effect of opening the three-membered ring of the epoxide compound, side reactions such as polymerization of the epoxide compound and polyisocyanate, polymerization of the epoxide compound and polyol, and epoxide compound proceed, and some epoxide compounds are
It is configured as a part of the urethane resin composition before addition polymerization of carbon dioxide gas.

That is, as shown in Examples, when a polyol component obtained by adding and mixing an epoxide compound and an addition reaction catalyst and an isocyanate component are mixed and stirred to produce a foamed heat insulating material, not less than a small amount of polyol in the raw material is produced. The foamed heat insulating material obtained has a structure in which a urethane resin and an epoxy resin are combined in a complex manner. For this reason,
The resin thermal conductivity of the foam insulation deteriorates under the influence of the thermal conductivity of the resin component composed of an epoxide compound having a small number of functional groups, and the gas thermal conductivity is sufficiently reduced even when carbon dioxide is removed by reaction. It is possible that the reduction effect cannot be exhibited.

Therefore, the resin thermal conductivity of a urethane resin composed of a mixture of epoxide compounds and polyisocyanates, epoxide compounds and polyols, and by-products such as polymerization of epoxide compounds does not deteriorate, and the urethane resin does not deteriorate. The foamed heat insulating material has an excellent heat insulating performance by rapidly reacting and fixing the carbon dioxide inside the bubbles of the foamed heat insulating material and improving the gas thermal conductivity, thereby improving the heat insulating performance of the foamed heat insulating material. And it was a subject to obtain a heat insulation box.

In view of the above problems, the present invention suppresses the side reaction of an epoxide compound promoted by an addition reaction catalyst between an epoxide compound and carbon dioxide in an injection and foaming step, and comprises a mixture of by-products of the epoxide compound. The resin component does not deteriorate the thermal conductivity of the resin, the remaining epoxy groups quickly fix the carbon dioxide, and improve the heat insulating performance of the foam heat insulating material. It is an object of the present invention to provide a method for manufacturing a heat insulating material.

In addition, a side reaction of the epoxide compound promoted by an addition reaction catalyst of the epoxide compound and carbon dioxide in the injection foaming stage is suppressed, and the resin component composed of the by-products of the epoxide compound is mixed with the resin thermal conductivity. Provide a heat-insulating box with excellent heat-insulating performance that improves the heat-insulating performance of the heat-insulating box by filling the foamed heat-insulating material with the remaining epoxy groups immobilizing carbon dioxide quickly without reducing the rate. It is intended to do so.

[0010]

In order to solve the above-mentioned problems, the present invention comprises a foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, and comprises at least a urethane bond and a urea bond. In a resin composition containing, a carbonate synthesis catalyst coated with a resin film,
It contains a carbonate compound formed by reacting an epoxide compound and carbon dioxide.

Further, the carbonate synthesis catalyst contains at least a halogenated onium salt.

Further, the carbonate synthesis catalyst contains at least a complex of an onium halide salt and an alkali metal halide.

Further, the carbonate synthesis catalyst is a solid powder having a maximum particle size of 0.5 mm or less.

According to the present invention, the side reaction of the epoxide compound is suppressed, the resin thermal conductivity of the obtained foamed insulating material is not deteriorated, and the gas component inside the closed cells of the foamed insulating material is volatile. A foam heat insulating material having excellent heat insulating performance, which is filled with a foaming agent and has a very low partial pressure of carbon dioxide having a high gas thermal conductivity, is obtained.

[0015] The method for producing a foamed heat insulating material of the present invention comprises:
Polyol, foam stabilizer, catalyst, reactive foaming agent, volatile foaming agent, polyisocyanate, epoxide compound, and a carbonate synthesis catalyst coated with a resin film are mixed and foamed. Carbon dioxide gas generated by the reaction between the reactive foaming agent and the polyisocyanate inside the bubbles,
Forming a foamed polyurethane resin composition containing a volatile foaming agent, and adsorbing carbon dioxide gas in closed cells of the foamed polyurethane resin composition in the presence of a carbonate synthesis catalyst in which the epoxide compound is coated with a resin film. Forming a carbonate compound, and substantially filling the inside of the closed cells with a volatile foaming agent.

Further, the carbonate synthesis catalyst comprises at least a halogenated onium salt.

Further, the carbonate synthesis catalyst contains at least a complex of an onium halide salt and an alkali metal halide.

Further, the carbonate synthesis catalyst is a solid powder having a maximum particle size of 0.5 mm or less.

Further, the epoxide compound has a viscosity at 25 ° C. of 1,000 mPa · s or less.

According to the present invention, the side reaction of the epoxide compound is suppressed, the resin thermal conductivity of the obtained foamed heat insulating material is not deteriorated, and the gas component inside the closed cells of the foamed heat insulating material is volatile. It is possible to provide a method for producing a foamed heat insulating material which is filled with a foaming agent and has a very low partial pressure of carbon dioxide having a high gas thermal conductivity and an excellent heat insulating performance.

Further, the heat insulating box of the present invention includes a space formed by a first wall member, a second wall member, 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 in a resin composition containing at least a urethane bond and a urea bond, a carbonate synthesis catalyst coated with a resin film, and an epoxide compound And a carbonate compound formed by reacting carbon dioxide with carbon dioxide.

Further, the carbonate synthesis catalyst comprises at least a halogenated onium salt.

Further, the carbonate synthesis catalyst comprises at least a complex of an onium halide salt and an alkali metal halide.

Further, the carbonate synthesis catalyst is a solid powder having a maximum particle size of 0.5 mm or less.

According to the present invention, the side reaction of the epoxide compound is suppressed, the resin thermal conductivity of the obtained foamed insulating material is not deteriorated, and the gas component inside the closed cells of the foamed insulating material is volatile. A heat-insulating box with excellent heat-insulating performance, which is filled with a foaming agent and has a very low partial pressure of carbon dioxide having a high gas thermal conductivity, can be obtained.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The foamed heat insulating material according to the first aspect of the present invention comprises a foamed polyurethane resin composition having closed cells filled with a volatile foaming agent, and has at least a urethane bond and a urea bond. In a resin composition containing, a carbonate synthesis catalyst coated with a resin film, and a carbonate compound formed by reacting carbon dioxide gas with an epoxide compound, characterized in that the excellent heat insulating performance A foamed heat insulating material is obtained.

With the above structure, the epoxide compound added as a raw material reacts with the carbon dioxide gas remaining inside the closed cells after the foamed heat insulating material is formed by the action of the carbonate synthesis catalyst covered with the resin film, Form a carbonate compound. This makes it possible to substantially fill the gas components remaining inside the closed cells with the volatile foaming agent.

On the other hand, since the carbonate synthesis catalyst is coated with the resin film, the epoxide compound on the outside of the resin film is not activated, and a side reaction with isocyanate or polyol can be suppressed. It is possible to reduce the deterioration of the resin thermal conductivity of the foamed heat insulating material.

Further, since the carbon dioxide gas remaining inside the closed cells exists as a gas, the carbon dioxide gas easily permeates the resin film of the carbonate synthesis catalyst, reacts promptly with the activated epoxide compound impregnated into the inside, and reacts with the carbonate compound. Does not inhibit the formation of

The foamed heat insulating material according to the second aspect of the present invention comprises:
The carbonate synthesis catalyst is characterized by containing at least a halogenated onium salt, wherein the gas component inside the closed cells of the foam insulation is filled with a volatile foaming agent,
A foam heat insulating material having excellent heat insulating performance and a very low partial pressure of carbon dioxide having a high gas thermal conductivity can be obtained.

With the above structure, the carbonate synthesis catalyst comprising an onium halide salt coated with the resin film added as a raw material is soluble in the polyol component in the urethane raw material, but is not coated with the resin film. Therefore, elution into the urethane raw material can be suppressed. As a result, a side reaction with an isocyanate or a polyol can be suppressed without activating the epoxide compound outside the resin film, and the resin thermal conductivity of the obtained foamed heat insulating material does not deteriorate.

The foamed heat insulating material according to the third aspect of the present invention comprises:
The carbonate synthesis catalyst is characterized in that it contains at least a complex of an onium halide salt and an alkali metal halide, and the gas component inside the closed cells of the foamed insulating material is filled with a volatile foaming agent, A foam heat insulating material having excellent heat insulating performance and a very low partial pressure of carbon dioxide having a high thermal conductivity can be obtained.

With the above structure, a carbonate synthesis catalyst comprising a complex of an onium halide salt and an alkali metal halide coated with a resin film added as a raw material is soluble in a polyol component in a urethane raw material. Since it is covered with a resin film, elution into urethane raw materials can be suppressed. As a result, without activating the epoxide compound outside the resin film,
A side reaction with isocyanate or polyol can be suppressed, and the resin thermal conductivity of the obtained foamed heat insulating material does not deteriorate. In addition, the alkali metal halide, which activates the urethane reaction by dissolving it in the urethane raw material, elutes into the raw material, does not affect the urethane reaction, and promotes the formation of carbonate after the foam insulation is formed. can do.

The foam insulating material according to the fourth aspect of the present invention comprises:
The carbonate synthesis catalyst is a solid powder having a maximum particle size of 0.5 mm or less. The gas component inside the closed cells of the foamed heat insulating material is filled with a volatile foaming agent, and the gas thermal conductivity is increased. Thus, a foamed heat insulating material having an excellent heat insulating performance and an extremely low partial pressure of carbon dioxide having a large value can be obtained.

With the above structure, the carbonate synthesis catalyst coated with the resin film to be added as a raw material is a solid powder having a maximum particle size of 0.5 mm or less. There is no problem that carbon dioxide gas is dispersed in the substance and remains locally.
In addition, there are few problems such as foam breakage due to the solid component being buried in the resin composition, and there is little effect of deteriorating the resin thermal conductivity.

[0036] The method for producing a foamed heat insulating material according to claim 5 of the present invention is a method for producing a foamed heat insulating material, comprising: a polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, a polyisocyanate, and an epoxide compound. , A foamed polyurethane resin containing a carbonate synthesis catalyst coated with a resin film, foamed, and containing a carbon dioxide gas generated by the reaction of a reactive foaming agent and a polyisocyanate inside a closed cell, and a volatile foaming agent Forming a composition, wherein the epoxide compound adsorbs carbon dioxide in closed cells of the foamed polyurethane resin composition in the presence of a carbonate synthesis catalyst coated with a resin film to form a carbonate compound, Substantially filling the inside of the cells with a volatile foaming agent, wherein the gas component inside the closed cells of the foamed insulating material is a volatile foaming agent. Tasa is, a very low partial pressure of greater carbon dioxide gas thermal conductivity, foam insulation can be obtained with excellent heat insulation performance.

According to the above configuration, in the step of forming the urethane resin composition, the epoxide compound added as a raw material has low activity with respect to the reactive blowing agent, and generates carbon dioxide gas by the reaction between the reactive blowing agent and the polyisocyanate. It does not inhibit development. Further, since the reaction between the epoxide compound and the carbon dioxide gas proceeds more slowly than the reaction for generating the carbon dioxide gas, the generated carbon dioxide gas can contribute to the formation of closed cells of the foamed heat insulating material. On the other hand, the carbonate synthesis catalyst coated with the resin film does not activate the epoxide compound outside the resin film, can suppress the side reaction with the isocyanate or the polyol, and obtains the foamed heat insulating material. The deterioration of the resin thermal conductivity is small.

In the step after the formation of the urethane resin composition, the epoxide compound reacts with the carbon dioxide gas remaining inside the closed cells by the action of the carbonate synthesis catalyst coated with the resin film to form the carbonate compound. I do. This makes it possible to substantially fill the gas components remaining inside the closed cells with the volatile foaming agent. In addition, since the carbon dioxide gas inside the closed cells exists as a gas, it easily permeates through the resin film of the carbonate synthesis catalyst,
It reacts promptly with the activated epoxide compound impregnated into the interior and does not inhibit the formation of the carbonate compound.

A method for producing a foamed heat insulating material according to a sixth aspect of the present invention is characterized in that the carbonate synthesis catalyst contains at least a halogenated onium salt, and the gas inside the closed cells of the foamed heat insulating material is provided. The components are filled with a volatile foaming agent, so that a foamed heat insulating material having excellent heat insulating performance and a very low partial pressure of carbon dioxide having a high gas thermal conductivity can be obtained.

According to the above configuration, in the step of forming the urethane resin composition, the carbonate synthesis catalyst comprising an onium halide salt added as a raw material is soluble in the polyol component in the urethane raw material.
Since it is covered with the resin film, elution into the urethane raw material can be suppressed. As a result, without activating the epoxide compound outside the resin film, side reactions with isocyanates and polyols can be suppressed,
The resin thermal conductivity of the obtained foam insulation does not deteriorate.

A method for producing a foamed heat insulating material according to claim 7 of the present invention is characterized in that the carbonate synthesis catalyst contains at least a complex of an onium halide salt and an alkali metal halide. The gas component inside the closed cells of the heat insulating material is filled with the volatile foaming agent, so that a foamed heat insulating material having excellent heat insulating performance and having a very low partial pressure of carbon dioxide having a high gas thermal conductivity can be obtained.

According to the above configuration, in the step of forming the urethane resin composition, the carbonate synthesis catalyst comprising a complex of an onium halide salt and an alkali metal halide added as a raw material is soluble in the polyol component in the urethane raw material. However, since it is covered with the resin film, elution into the urethane raw material can be suppressed. As a result, a side reaction with an isocyanate or a polyol can be suppressed without activating the epoxide compound outside the resin film, and the resin thermal conductivity of the obtained foamed heat insulating material does not deteriorate. In addition, the property of the alkali metal halide to highly activate the urethane reaction can be suppressed, and the influence on productivity such as demolding property is small.

In the method for producing a foamed heat insulating material according to claim 8 of the present invention, the carbonate synthesis catalyst has a maximum particle size of 0.5 m
m or less solid powder,
The gas component inside the closed cells of the foamed heat insulating material is filled with a volatile foaming agent, and a foamed heat insulating material having an excellent heat insulating performance and a very low partial pressure of carbon dioxide having a high gas thermal conductivity can be obtained.

According to the above configuration, in the step of forming the urethane resin composition, the carbonate synthesis catalyst added as a raw material is a solid powder having a maximum particle size of 0.5 mm or less, so that it is relatively uniform even when it is not dissolved in the raw material. Can be dispersed in the resin composition. Also, there are few problems such as foam breakage caused by embedding the solid component in the resin composition.

In the method for producing a foamed heat insulating material according to the ninth aspect of the present invention, the epoxide compound may be 1,0 at 25 ° C.
The gas component inside the closed cells of the foamed heat insulating material is filled with a volatile foaming agent, and the partial pressure of carbon dioxide gas having a large gas thermal conductivity is extremely low. A foam insulating material having low and excellent heat insulating performance is obtained.

According to the above configuration, in the step after the formation of the urethane resin composition, the epoxide compound added as a raw material has a viscosity of not more than 1,000 mPa · s at 25 ° C., and is impregnated into the resin composition. Along with
It is easy to impregnate into the carbonate synthesis catalyst coated with the resin film, and it is possible to promote the formation of carbonate.

The heat insulating box according to claim 10 of the present invention comprises:
A first wall member, a second wall member, and 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 in a resin composition containing at least a urethane bond and a urea bond, a carbonate synthesis catalyst coated with a resin film, and an epoxide compound And a carbonate compound formed by reacting carbon dioxide gas.The gas component inside the closed cells of the foamed heat insulating material filled in the heat insulating box is filled with a volatile foaming agent, A heat insulating box having excellent heat insulating performance and having a very low partial pressure of carbon dioxide having a high gas thermal conductivity can be obtained.

The heat insulating box according to claim 11 of the present invention comprises:
The carbonate synthesis catalyst contains at least a halogenated onium salt, and the gas component inside the closed cells of the foamed heat insulating material filled in the heat insulating box is filled with a volatile blowing agent, A heat insulating box having excellent heat insulating performance and a very low partial pressure of carbon dioxide having high conductivity can be obtained.

The heat insulating box according to the twelfth aspect of the present invention comprises:
The carbonate synthesis catalyst contains at least a complex of an onium halide salt and an alkali metal halide, and the gas component inside the closed cells of the foam insulation filled in the insulation box is volatile. A heat-insulating box with excellent heat-insulating performance, which is filled with a foaming agent and has a very low partial pressure of carbon dioxide having a high gas thermal conductivity, can be obtained.

The heat-insulating box according to claim 13 of the present invention comprises:
The carbonate synthesis catalyst is a solid powder having a maximum particle size of 0.5 mm or less, and the gas component inside the closed cells of the foamed heat insulating material filled in the heat insulating box is a volatile foaming agent. A heat-insulating box having excellent heat-insulating performance, which is filled and has a very low partial pressure of carbon dioxide having a high gas thermal conductivity, can be obtained.

Hereinafter, an embodiment of the present invention will be described with reference to FIGS. (Embodiment 1) FIG. 1 is a perspective view, partially cut away, of a heat insulating box according to an embodiment of the present invention.
Denotes a heat insulating box, and a polyurethane resin composition is used to fill a space formed by a first wall member 2 which is a vacuum formed body of an ABS resin composition and a second wall member 3 formed by processing a steel plate. The foamed heat insulating material 4 is filled and buried.

FIG. 2 is a schematic view of a foamed heat insulating material according to one embodiment of the present invention. In the drawing, reference numeral 4 denotes a foamed heat insulating material, and urethane formed mainly by a reaction between an isocyanate and a polyol composition. A closed cell 6 is formed by a resin skeleton 5 comprising a bond, a urea bond formed by reacting isocyanate with water as a reactive foaming agent, and a carbonate compound formed by reacting an epoxide compound with carbon dioxide. , On the wall surface or resin skeleton of the closed cell 6,
The carbonate synthesis catalyst 7 covered with the resin film is dispersed and filled with a volatile foaming agent.

(Embodiment 2) In the method for manufacturing the foamed heat insulating material 4 shown in FIG. 1, a polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, and a resin film are coated. The mixed carbonate synthesis catalyst is mixed in advance to obtain a premix component A.

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

Further, the constituent materials of the present invention will be described in detail. As the carbonate synthesis catalyst of the present invention,
It is preferable to use a powder of a nucleophilic compound which has been previously coated with a resin film. As the compound having nucleophilicity, a halogen ion is effective.
Compounds in which a halogen ion is a counter ion of an onium salt or an alkali halide are preferred. Specifically, a tetraalkylammonium halide salt or a tetraalkylphosphonium halide salt is particularly preferred, and the alkyl group is not particularly limited.

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

Further, a compound having an electrophilic property can be used in combination. As the electrophilic compound, Lewis acidic metal halides, organotin halides, organotin fatty acid esters and the like are preferred, and specifically, zinc halides such as zinc chloride, zinc bromide, zinc iodide, and Is particularly preferably dibutyltin dilaurate.

Further, examples of the resin film of the present invention include an ethyl cellulose film, a film mainly composed of acrylic, a film mainly composed of vinyl acetate, a film mainly composed of urethane, and a film mainly composed of silicone. The same effect can be obtained as long as the resin film allows the passage of carbon dioxide gas. Preferably, the epoxide compound is impregnated,
If the material breaks down the coating over time, the synthesis of carbonate is promoted.

The particle size of the carbonate synthesis catalyst is preferably 0.5 mm or less at the maximum from the viewpoints of dispersibility in the foamed heat insulating material and promoting the reaction rate between the epoxide compound and carbon dioxide gas.

By applying the carbonate synthesis catalyst coated with the above resin film, in the step of forming the urethane resin composition, it is possible to suppress undesired side reactions, And an epoxide compound are subjected to an addition reaction, whereby a liquid or solid cyclic carbonate composition can be synthesized. At least in the presence of an onium salt, the reaction easily proceeds at normal temperature and normal pressure.

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.

Further, from the viewpoint of improving the strength of the foamed heat insulating material,
Polyglycidyl ethers such as neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, and various epoxy resins represented by polycondensation products of bis-phenol A and epichlorohydrin are preferred.

As glycidylamines, grade 604 manufactured by Yuka Shell Epoxy Co., Ltd. represented by polyglycidylamine type epoxy resin, and Sumitomo Chemical Co., Ltd.
Grade ELM-120 manufactured by the company.

The glycerol ethers include
Glycidol, glycerol polyglycidyl ether and the like.

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

Further, the epoxide compound of the present invention comprises 25
The viscosity is preferably 1,000 mPa · s or less at ℃, and the impregnation of the carbonate synthesis catalyst coated with the resin film can proceed more quickly.

The reactive foaming agent of the present invention includes:
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 a main foaming agent of the resin composition, and is a compound having good compatibility with the polyol composition and having 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 and applied.

[0071]

The foamed heat insulating material of the present invention will be described below with reference to examples.

(Example 1) The polyol had a hydroxyl value of 46.
5 mg KOH / g of a tolylenediamine-based polyether polyol, a foam stabilizer is a silicone-based surfactant, F-337 manufactured by Shin-Etsu Chemical Co., Ltd., and a catalyst is dimethylcyclohexylamine. ) Manufactured by Kaolinizer No. Sample No. 10 was prepared by coating a resin film in advance with water as a reactive blowing agent, cyclopentane as a volatile blowing agent, and tetra-n-butylammonium bromide as a carbonate synthesis catalyst A. The above ingredients are mixed in a predetermined blending number, and a premix component A
It was constituted as.

The resin coating of the carbonate synthesis catalyst A was prepared by using a centrifugal flow type coating granulator made by Freund Corporation with a resin containing ethyl cellulose as a main component as a binder, and further using the same apparatus to form an average film. 2μm thick
Was formed. The average particle size of the obtained carbonate synthesis catalyst A was 0.4 mm, the maximum particle size was 1 mm, and 0.5 m
The content of the powder having a particle size of m or more was 25%.

As the epoxide compound of Component B, phenyl glycidyl ether manufactured by NOF Corporation was used.

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

The premixed component A, the component B composed of an epoxide compound, and the component C composed of an isocyanate thus mixed and mixed are mixed and stirred in a predetermined mixing number, and foamed by a high-pressure foaming machine. And a second wall member to form a heat insulating box. In addition, the filling density of the foamed insulating material is such that the average density of the core portion is 38 kg /.
It was adjusted to m ^3.

(Example 2) As a carbonate synthesis catalyst B, tetra-n-butylammonium bromide and zinc chloride were dissolved in ethyl alcohol at a molar equivalent ratio of 2: 1 and recrystallized to obtain a complex, which was previously coated on a resin film. A heat-insulated box was obtained in the same manner as in Example 1 except for using the coated material.

The resin film of the carbonate synthesis catalyst B was formed in the same manner as in Example 1. The average thickness of the obtained carbonate synthesis catalyst B was 2 μm, the average particle size was 0.4 mm, and the maximum particle size was 0.4 mm. The diameter was 1 mm, and the content of powder having a particle size of 0.5 mm or more was 25%.

Example 3 Using the same raw materials as in Example 1, a carbonate synthesis catalyst C was previously coated with tetra-n-butylammonium bromide with a resin film, the average film thickness was 2 μm, and the average particle size was 0.1 μm. 3mm,
A heat insulating box having a maximum particle size of 0.5 mm was obtained.

The rigid urethane foam of the heat-insulated box obtained in this manner was cut out, and the heat conductivity after one day, one week, and one month after foaming, the amount of carbon dioxide in the bubbles, and the charged amount of the raw materials were measured. The remaining amount of the epoxy group and the amount of carbonate produced were measured, and the measurement results are shown in (Table 1). The thermal conductivity was measured by AUTO-Λ manufactured by Eiko Seiki Co., Ltd., the amount of carbon dioxide was measured by gas chromatography manufactured by Shimadzu Corporation, and the remaining amount of epoxy group and the amount of carbonate were calculated by ( It was measured by liquid chromatography manufactured by Shimadzu Corporation.

At the same time, as a comparative example, when the same raw material as in Example 1 was used and tetra-n-butylammonium bromide was added as the carbonate synthesis catalyst D without coating with a resin film (Comparative Example A), Using the same raw materials as in Example 2, tetra-n-butylammonium bromide and zinc chloride were used as the carbonate synthesis catalyst E:
When a complex obtained by dissolving in ethyl alcohol at a molar equivalent ratio and recrystallization is added without coating with a resin film (Comparative Example B), the epoxide compound of Component B is a polyglycidyl ether. Using Asahi Denka Kogyo Co., Ltd. bis-phenol A type epoxy resin EP-4300,
Other raw materials are shown in (Table 1) in the same manner as in Example 1 (Comparative Example C).

[0082]

[Table 1]

As described above, in the foamed heat insulating material of Example 1 of the present invention, the phenylglycidyl ether used as the epoxide compound added as a raw material reacts with carbon dioxide, so that the gas component inside the closed cells of the foamed heat insulating material is reduced. It was found that a foam insulating material filled with cyclopentane as a volatile foaming agent and having excellent heat insulating performance and a heat insulating box were obtained.

This is because phenyl glycidyl ether, which is an epoxide compound that reacts with carbon dioxide, is formed by the action of tetra-n-butylammonium bromide coated with a resin film, which is a carbonate synthesis catalyst A, after the foamed heat insulating material is formed. Reacts with carbon dioxide remaining inside the closed cells to form a carbonate compound. This makes it possible to substantially fill the gas components remaining inside the closed cells with the volatile foaming agent.

Further, since the carbonate synthesis catalyst A is covered with the resin film, in the step of forming the urethane resin composition, the epoxide compound outside the resin film is not activated, and the reaction with the isocyanate or polyol is not performed. The side reaction can be suppressed, the residual amount of the epoxide compound effective for carbonate generation can be increased, and the deterioration of the resin thermal conductivity of the foamed heat insulating material due to the side reaction is small, and the heat conduction of the foamed heat insulating material is reduced. We think that the rate could be improved.

Since the carbon dioxide gas remaining inside the closed cells exists as a gas, the carbonate synthesis catalyst A
And easily reacted with the epoxide compound which was impregnated and activated inside, and did not inhibit the formation of the carbonate compound.

The foamed heat insulating material of Example 2 of the present invention was obtained by dissolving tetra-n-butylammonium bromide and zinc chloride in ethyl alcohol as a carbonate synthesis catalyst B at a molar equivalent ratio of 2: 1 and recrystallization. The gas component inside the closed cells of the foamed heat insulating material is filled with cyclopentane, which is a volatile foaming agent, using a foamed heat insulating material having excellent heat insulating performance, And it turned out that a heat insulation box is obtained.

This is considered to be due to the same effect as in the first embodiment. Furthermore, the zinc chloride contained in the carbonate synthesis catalyst B coated with the resin film added as a raw material also highly activates the urethane reaction when dissolved in the urethane raw material, but since it is coated with the resin film, It is considered that the formation of the carbonate was able to be promoted after the foamed heat insulating material was formed without any influence on the urethane reaction due to the elution into the urethane raw material.

The foam insulating material of Example 3 of the present invention has a maximum particle size of 0.5 m as the carbonate synthesis catalyst C.
By using tetra-n-butylammonium bromide of m or less, even when it is not dissolved in the raw material, it can be relatively uniformly dispersed in the resin composition, and there is no problem that carbon dioxide gas remains locally. Also,
There were few problems such as foam breakage due to the solid component being buried in the resin composition, and there was no effect of deteriorating the thermal conductivity of the resin.

In the comparative example, when the same raw material as in Example 1 was used and tetra-n-butylammonium bromide was added as the carbonate synthesis catalyst D without coating with a resin film (Comparative Example A), the urethane resin was used. It was found that the residual amount of the epoxide compound reacting with carbon dioxide gas after the formation of the composition was extremely small, and it was not possible to leave the amount necessary to remove all the carbon dioxide gas by reaction over time.

Further, the thermal conductivity of the obtained foamed insulating material is as follows:
Even at the stage where the carbon dioxide gas is reduced, the decrease in the thermal conductivity is small, which is considered to be due to the deterioration of the thermal conductivity of the resin due to the side reaction of the epoxide compound.

Further, a complex obtained by dissolving tetra-n-butylammonium bromide and zinc chloride in ethyl alcohol at a molar equivalent ratio of 2: 1 as a carbonate synthesis catalyst E using the same raw materials as in Example 2 and recrystallizing the same. Was added without coating with a resin film (Comparative Example B), zinc chloride was eluted into the urethane raw material, the reactivity became extremely fast, and it was not possible to fill the heat insulating box.

As the epoxide compound of the component B,
In the case where bis-phenol A type epoxy resin EP-4300 manufactured by Asahi Denka Kogyo Co., Ltd., which is a polyglycidyl ether, was used and the other raw materials were the same as in Example 1 (Comparative Example C), carbon dioxide gas Although the epoxide compound required for the reaction remained, the reaction rate was slowed and carbon dioxide in the foamed heat insulating material could not be completely removed even after one month of aging.

This may be due to the difference in the reaction activity between the epoxide compound and the carbon dioxide gas. The polyglycidyl ether bis-phenol A type epoxy resin EP-4300 manufactured by Asahi Denka Kogyo KK at 25 ° C. Is 9,000 to 11,000 mPa · s,
This is considered to be due to the reduced chance of contact with the carbonate synthesis catalyst A coated with the resin film after the formation of the foamed heat insulating material.

[0095]

As described above, according to the present invention, the epoxide compound added as a raw material remains in the closed cells after the foamed heat insulating material is formed due to the action of the carbonate synthesis catalyst coated with the resin film. Reacts with carbon dioxide to form carbonate compounds. This makes it possible to substantially fill the gas components remaining inside the closed cells with the volatile foaming agent.

Further, since the carbonate synthesis catalyst is coated with the resin film, the epoxide compound on the outside of the resin film is not activated, and a side reaction with isocyanate or polyol can be suppressed. It is possible to reduce the deterioration of the resin thermal conductivity of the foamed heat insulating material. In addition, since the carbon dioxide gas remaining inside the closed cells exists as a gas, the carbon dioxide gas easily permeates through the resin film of the carbonate synthesis catalyst, and quickly reacts with the activated epoxide compound impregnated into the inside to form a carbonate compound. It does not inhibit.

[Brief description of the 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 Signs] 1 foam insulation material 2 first wall member 3 second wall member 4 foam insulation material 5 resin skeleton 6 closed cell 7 carbonate synthesis catalyst

Claims (13)

[Claims] 1. A carbonate comprising 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 coated with a resin film in a resin composition. A synthesis catalyst,
A foam heat insulating material comprising a carbonate compound formed by reacting an epoxide compound and carbon dioxide. 2. The foam insulation material according to claim 1, wherein the carbonate synthesis catalyst contains at least a halogenated onium salt. 3. The foamed heat insulating material according to claim 1, wherein the carbonate synthesis catalyst contains at least a complex of an onium halide salt and an alkali metal halide. 4. The carbonate synthesis catalyst has a maximum particle size of 0.1.
2. A solid powder of not more than 5 mm.
The foam insulation material according to any one of claims 1 to 3. 5. A polyol, a foam stabilizer, a catalyst, a reactive foaming agent, a volatile foaming agent, a polyisocyanate,
An epoxide compound and a carbonate synthesis catalyst coated with a resin film are mixed and foamed, and the closed foam contains carbon dioxide gas generated by a reaction between a reactive foaming agent and a polyisocyanate, and a volatile foaming agent. Forming a foamed polyurethane resin composition, and forming a carbonate compound by adsorbing carbon dioxide gas in closed cells of the foamed polyurethane resin composition in the presence of a carbonate synthesis catalyst in which the epoxide compound is coated with a resin film. Filling the inside of the closed cells substantially with a volatile foaming agent. 6. The method according to claim 5, wherein the carbonate synthesis catalyst contains at least a halogenated onium salt. 7. The method for producing a foamed heat insulating material according to claim 5, wherein the carbonate synthesis catalyst contains at least a complex of an onium halide salt and an alkali metal halide. 8. The carbonate synthesis catalyst has a maximum particle size of 0.1.
6. A solid powder having a size of 5 mm or less.
A method for producing a foamed heat insulating material according to any one of claims 1 to 7. 9. The method for producing a foamed heat insulating material according to claim 5, wherein the epoxide compound has a viscosity of not more than 1,000 mPa · s at 25 ° C. 10. A space formed by a first wall member, a second wall member, the first wall member, and the second wall member is filled with a volatile foaming agent. Filled with a foamed polyurethane resin composition having closed cells, at least a urethane bond, and a resin composition containing a urea bond, a carbonate synthesis catalyst coated with a resin film, an epoxide compound and carbon dioxide react with each other. A heat-insulating box comprising a carbonate compound. 11. The carbonate synthesis catalyst according to claim 1, wherein at least a halogenated onium salt is contained.
The heat-insulated box according to 0. 12. The heat insulating box according to claim 10, wherein the carbonate synthesis catalyst contains at least a complex of an onium halide salt and an alkali metal halide. 13. The heat insulating box according to claim 10, wherein the carbonate synthesis catalyst is a solid powder having a maximum particle size of 0.5 mm or less.