JPH0797421A - Expanded heat-insulation material and heatinsulation box - Google Patents

Abstract

PURPOSE:To obtain the title material which does not suffer from a dispersion of density due to, e.g. the separation of a blowing agent, and has a quality equivalent to that of a heat-insulation material prepared by using a conventional halohydrocarbon as the blowing agent even when an aliphatic or cyclic hydrocarbon poorly compatible with a polyol as the raw material of a urethane resin is used as the blowing agent and contributes the solution of the environmental problem of ozonosphere depletion. CONSTITUTION:The title material is prepared by mixing under agitation a polyol component containing at least 5% polyether polyol, obtained by the addition polymerization of ethylenediamine with an alkylene oxide, with an organic polyisocyanate, a foam stabilizer, a catalyst and a blowing agent consisting of at least an aliphatic or cyclic hydrocarbon of a boiling point of 80 deg.C or below, and the title box is made by packing the above material into the space between the inner and outer boxes by in-situ foaming.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foam insulation material used in refrigerators, freezers and the like, and a heat insulation box body filled with the foam insulation material.

[0002]

2. Description of the Related Art In recent years, chlorofluorocarbons (hereinafter C
Environmental problems such as ozone depletion and global warming due to the influence of (FC) are attracting attention, and in manufacturing a hard urethane foam, which is a typical foam insulation material, C
For the purpose of reducing the amount of FC used, a method of using carbon dioxide gas obtained by the reaction of organic polyisocyanate and water as a part of a foaming agent, or an alternative substance of CFC, which has little effect on ozone destruction2, Foaming with 2-dichloro-1,1,1-trifluoroethane and 1,1-dichloro-1-fluoroethane, foaming with hydrocarbons such as n-pentane that does not have any effect on ozone destruction because it does not contain halogen elements, etc. Various improvement efforts are being considered.

For example, pages 197 to 201 of a collection of papers presented at the Polyurethane International Forum '93 held from May 10 to 12, 1993 (Gerhard Heilig, yos
hinori Kihara, 1993. "Pentane Blown Rigid Foam")
Describes a heat insulating material using a hydrocarbon such as n-pentane, which has no effect on ozone destruction, as a foaming agent.

[0004]

However, as mentioned in this document, when a hydrocarbon such as n-pentane is used as a blowing agent, it is a conventional technique.
Compared to the case where a halogenated hydrocarbon such as FC or HCFC is used as a foaming agent, the mutual solubility with the urethane raw material polyol is poor, and the density of the foaming agent is separated by separating in the raw material tank of the high pressure foaming machine. There was a problem that there were variations and it was not possible to obtain foamed products of constant quality.Because the number of hydrocarbon foaming agents added was small, a foamed insulation material with a density suitable for filling the heat-insulating box was used. In order to obtain it, it is necessary to add an auxiliary foaming agent such as water more than necessary, and carbon dioxide gas having a large gas thermal conductivity remains excessively in the bubbles of the obtained foamed heat insulating material. It has drawbacks such as poor heat insulation performance.

Therefore, even when a hydrocarbon such as n-pentane is used as a foaming agent, a foamed heat insulating material having a constant quality with no density variation can be obtained and energy saving can be achieved.
From the standpoint of improvement, it has been a problem to produce a foamed heat insulating material which has the same heat insulating performance as a halogenated hydrocarbon type foaming agent which is a conventional foaming agent and which does not affect global environmental problems.

In view of the above problems, the present invention uses a hydrocarbon such as n-pentane, which has no influence on ozone layer depletion, as a foaming agent and is a conventional foaming agent, CFC11.
It is an object of the present invention to provide a stable quality foamed heat insulating material having a heat insulating performance equivalent to that of

[0007]

In order to solve the above problems, the present invention has a hydroxyl value of 350 to 650 mg KO obtained by addition-polymerizing alkylene oxide with ethylenediamine.
A polyol component containing at least 5% or more of H / g of polyetherpolyol, and an organic polyisocyanate,
A foam heat insulating material is obtained by mixing and stirring a foam stabilizer, a catalyst, and a foaming agent having at least one component of an aliphatic or cyclic hydrocarbon having a boiling point of 80 ° C. or less.

Further, the foamed heat insulating material is foamed and filled in a space portion constituted by an inner box and an outer box to obtain a heat insulating box body.

[0009]

With the above structure, a hydroxyl value of 350 is obtained by addition-polymerizing alkylene oxide with ethylenediamine.
Polyol component polyol containing at least 5% or more of polyether polyol of 650 mgKOH / g has very good mutual solubility with a hydrocarbon-based foaming agent and uniformly dissolves the foaming agent in the raw material components. Therefore, it is possible to obtain a foamed heat insulating material of a constant quality without problems such as separation in the raw material tank of the high-pressure foaming machine. Further, since the addition ratio of the hydrocarbon-based foaming agent can be increased, the number of auxiliary foaming agents such as water to be added can be reduced, and the gas thermal conductivity of the gas components remaining in the bubbles of the foamed heat insulating material is high. The ratio of carbon dioxide gas can be reduced, and the heat insulating performance of the foamed heat insulating material can be improved.

Further, aliphatic or cyclic hydrocarbons having a boiling point of 80 ° C. or lower have an ozone depletion potential of 0, and are capable of producing a foamed heat insulating material effective in protecting the global environment.

By filling the foamed heat insulating material to form a heat-insulating box, a product of a certain quality can be obtained in manufacturing, and a heat-insulating box made of a conventional halogenated hydrocarbon-based foaming agent is used. In comparison, there is no problem such as deterioration of heat insulation performance, and the quality as an excellent heat insulation box can be secured.

As the aliphatic or cyclic hydrocarbon having a boiling point of 80 ° C. or lower, n-pentane, cyclopentane, etc. can be used.

[0013]

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

Polyol A is a hydroxyl value of 400 mgKOH / which is obtained by addition-polymerizing propylene oxide with ethylenediamine.
Polyetherpolyol and polyol B of g are aromatic amine-based polyetherpolyol having a hydroxyl value of 460 mgKOH / g, catalyst is Kaolyzer No. 1 manufactured by Kao Corporation, and foam stabilizer is Shin-Etsu. Chemical Co., Ltd. Silicone Surfactant F-33
5. The foaming agent is water or n-pentane, and the respective raw materials are mixed in a predetermined mixing number to form a premix component. On the other hand, the isocyanate component is an organic polyisocyanate composed of a crude MDI having an amine equivalent of 135.

The premix component thus prepared and the isocyanate component are mixed in a predetermined mixing number, foamed by a high-pressure foaming machine, and filled in a box body composed of an inner box and an outer box,
An insulated box was obtained. The thermal conductivity of the heat insulating material and the variation in density at this time are shown in (Table 1).

At the same time, as a comparative example, when ethylenediamine-based polyether was not added (Comparative Example A-
1 and A-2) are shown in Table 1 at the same time.

[0017]

[Table 1]

As described above, the foamed heat insulating material of the present invention is a foamed heat insulating material foamed by a high-pressure foaming machine even when n-pentane, which has a poor mutual solubility with the urethane raw material polyol, is used as a foaming agent. You can keep the density constant,
It was found that a product of a certain quality can be obtained in the production of the heat insulation box, and that a foam insulation material having excellent performance equivalent to that of CFC11 which is a conventional halogenated hydrocarbon foaming agent can be obtained.

This is because the polyetherpolyol obtained by addition-polymerizing alkylene oxide to ethylenediamine added as a part of the polyol component has very good mutual solubility with a hydrocarbon type foaming agent, It is considered that the foaming agent can be uniformly dissolved in the raw material components.
As a result, there is no problem such as separation of the hydrocarbon-based foaming agent in the raw material tank of the high-pressure foaming machine, and it is possible to obtain a foam insulation of constant quality and increase the ratio of addition of the hydrocarbon-based foaming agent. This is because the number of auxiliary foaming agents such as water added can be reduced, and the proportion of carbon dioxide gas having a large gas thermal conductivity can be reduced among the gas components remaining in the bubbles of the foamed heat insulating material.

As described above, the foamed heat insulating material of the present invention uses the hydrocarbon-based foaming agent having no ozone depletion coefficient to contribute to the solution of environmental problems such as ozone layer depletion and the conventional halogenated hydrocarbon-based material. The excellent heat insulation performance equivalent to that of the foaming agent can contribute to quality improvement by energy saving.

The heat-insulating box filled with the foamed heat-insulating material can maintain a constant quality in manufacturing, and is excellent in the heat-insulating performance as compared with the conventional halogenated hydrocarbon-based foaming agent and is excellent. The quality as a heat-insulating box can be secured.

At the same time, when no ethylenediamine-based polyether was added as a comparative example and the same amount of the hydrocarbon-based foaming agent was added as in Comparative Example A-1, the high-pressure foaming machine was used. Since the density of the foamed heat insulating material cannot be kept constant, there are problems such as generation of an unfilled portion when the heat insulating box is filled and leakage of the foamed heat insulating material from the heat insulating box. In addition, as shown in Comparative Example A-2, when the amount of water as the auxiliary foaming agent was increased, the ratio of carbon dioxide gas in the bubbles was increased, and sufficient heat insulation performance could not be improved.

[0023]

As described above, the present invention comprises a polyol component containing at least 5% or more of a polyether polyol having a hydroxyl value of 350 to 650 mgKOH / g obtained by addition-polymerizing alkylene oxide with ethylenediamine, Organic polyisocyanate, foam stabilizer, catalyst, and boiling point of 80
Since a foaming heat insulating material is produced by mixing and stirring a foaming agent having at least one component of aliphatic or cyclic hydrocarbon at a temperature of not higher than 0 ° C., a polyether polyol obtained by addition-polymerizing alkylene oxide with ethylenediamine is Since it has excellent mutual solubility with hydrocarbon-based foaming agents and can dissolve the foaming agents uniformly in the raw material components, there is no problem such as separation in the raw material tank of the high-pressure foaming machine, and foaming of a certain quality is achieved. Insulation can be provided. Furthermore, since the addition ratio of the hydrocarbon-based foaming agent can be increased, the number of parts of the auxiliary foaming agent such as water added can be reduced, and carbon dioxide having a large gas thermal conductivity in the gas component remaining in the bubbles of the foamed heat insulating material can be reduced. The gas ratio can be reduced, and the heat insulating performance of the foam heat insulating material can be improved.

Further, aliphatic or cyclic hydrocarbons having a boiling point of 80 ° C. or less have an ozone depletion potential of 0, and are capable of producing a foamed heat insulating material effective in protecting the global environment.

Further, by filling the foamed heat insulating material to form a heat insulating box, a product of a certain quality can be obtained in the manufacturing process, and a heat insulating box manufactured by a conventional halogenated hydrocarbon type foaming agent is used. In comparison, there is no problem such as deterioration of heat insulation performance, and the quality as an excellent heat insulation box can be secured.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI technical display location C08G 101: 00) C08L 75:04 (72) Inventor Tomonao Ara Takada Hondori, Osaka Prefecture 3-22, Matsushita Cold Machinery Co., Ltd.

Claims (2)

[Claims] 1. A hydroxyl value of 350 to 650 mg KO obtained by addition-polymerizing alkylene oxide with ethylenediamine.
A polyol component containing at least 5% or more of H / g of polyetherpolyol, and an organic polyisocyanate,
A foamed heat insulating material produced by foaming by mixing and stirring a foam stabilizer, a catalyst, and a foaming agent having at least one component of an aliphatic or cyclic hydrocarbon having a boiling point of 80 ° C. or less. 2. A heat insulating box body comprising an outer box, an inner box, and the foamed heat insulating material according to claim 1, wherein the space formed by the outer box and the inner box is foam-filled.