JPH069816A - Foamed heat insulating material and heat insulating box material - Google Patents

Abstract

(57) [Summary] [Purpose] In a foam insulation material used for refrigerators, freezers, etc., and an insulation box body, HCFC123 and HCFC14
By adding PFA or HFC to 1b within a limited range, it is intended to reduce the foam thermal conductivity by refining the foam cell and to contribute to the elimination of the environmental problem of ozone layer destruction. [Structure] Organic polyisocyanate, polyol, foam stabilizer, catalyst, HCFC123, HCFC as blowing agent component
141b and its compound, PFA or HFC is added within a limited range, and mixed and stirred to form a foamed heat insulating material, and the foamed heat insulating material is foamed and filled between both inner and outer boxes. Insulated box body.

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 layer depletion and global warming due to the influence of (FC) are attracting attention, and in manufacturing rigid urethane foam, which is a typical foam insulation material, C
A method of using carbon dioxide gas obtained by the reaction of an organic polyisocyanate and water as a part of a foaming agent for the purpose of eliminating the use amount of FC, HCFC123 which is an alternative substance of CFC and has little influence on ozone destruction, and H
Various improvement measures such as foaming by CFC141b are being studied.

For example, HCFC123, as announced at "Explanatory Meeting in Law Concerning Protection of Ozone Layer by Regulation of Specific Substances" held by Industrial Pollution Control Association of Japan on July 15, 1988, When HCFC141b and HCFC141b are used as the foaming agent, the gas thermal conductivity of the foaming agent itself is much larger than that of CFC11 which has been conventionally used as the foaming agent, and there is a problem that the heat insulating performance of the foam heat insulating material is significantly reduced. Stated.

As described above, it is not easy to substitute HCFC123 and HCFC141b, which have little influence on the ozone layer depletion, as a foaming agent for the current rigid urethane foam, and there are many problems at present. .

[0005]

As described above, according to the conventional technology, the Industrial Pollution Control Association of Japan, “Act on the Protection of the Ozone Layer by Regulation of Specific Substances, etc.” was held on July 15, 1988. HCFC12, which has little impact on ozone layer depletion,
When 3 and HCFC141b are used as a foaming agent for the current rigid urethane foam, the gas thermal conductivity of the foaming agent itself is CFC11 which has been conventionally used as a foaming agent.
However, there is a problem that the heat insulating performance of the foamed heat insulating material is greatly reduced as compared with the above.

Therefore, HCFC123 and HCFC1
Even when 41b was used as a foaming agent, it was a problem to obtain a foam heat insulating material having the same heat insulating performance as the foam heat insulating material using conventional CFC11 as a foaming agent without impairing other physical properties. .

In view of the above problems, the present invention is directed to HCFC123 and HCFC1 which have little influence on global environmental problems.
It is an object of the present invention to provide an excellent foamed heat insulating material having no problem of deteriorating heat insulation performance even when a foaming agent such as 41b is used.

[0008]

In order to solve the above-mentioned problems, the present invention provides an organic polyisocyanate, a polyol,
Catalyst, mixture of fluorocarbon type surfactant and silicone type surfactant as foam stabilizer, HC as blowing agent component
FC123, HCFC141b, and a mixture thereof and perfluoroalkane of 2 to 60 mol% of the total number of foaming agents as an auxiliary foaming agent component are mixed and stirred to obtain a foamed heat insulating material formed by foaming.

The present invention further relates to an organic polyisocyanate,
A polyol, a catalyst, a mixture of a fluorocarbon-based surfactant and a silicone-based surfactant as a foam stabilizer, HCFC123 and HCFC141b as a foaming agent component, and 10 to 4 of the total number of foaming agent parts as the mixture and an auxiliary foaming agent component.
This is a mixture of 0 mol% of hydrofluorocarbon and agitated to obtain a foamed heat insulating material formed by foaming.

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.

[0011]

With the above structure, the perfluoroalkane and hydrofluorocarbon used as the auxiliary foaming agent component have very poor compatibility with the polyol component and are difficult to dissolve in the raw material. Therefore, the fluorocarbon-based surfactant used as the foam stabilizer uniformly emulsifies and disperses in the raw material as extremely fine nuclei.

Therefore, it is possible to obtain a foamed heat insulating material having a very fine cell based on the ultrafine nucleus. In addition, when the perfluoroalkane and hydrofluorocarbon are individually foamed, the foaming efficiency is poor and the foam density is increased, or the thermal insulation performance is deteriorated due to cell breakage. However, in combination with HCFC123, HCFC141b, and a mixture thereof, Because of foaming, it is possible to obtain a good foamed heat insulating material having uniform and fine cells without increasing the foam density.

Therefore, the foam heat conductivity can be greatly reduced by improving the heat insulation performance by reducing the radiant heat conductivity accompanying the cell miniaturization. At this time, the perfluoroalkane and hydrofluorocarbon, which have a higher gas thermal conductivity than the main blowing agent component, are present as a mixed gas in the cell, but the amount of volatilization during the foaming process is large, and 60% of all blowing agent components If it is mixed at about mol%, the influence of the auxiliary foaming agent components such as perfluoroalkane and hydrofluorocarbon on the gas thermal conductivity is also small, and the contribution of the improvement of the thermal insulation performance by the reduction of the radiant thermal conductivity is greater. Become.

By filling the foamed heat insulating material to form a heat insulating box, almost no void is generated,
The quality as an excellent heat insulating box can be secured.

Further, perfluoroalkanes and hydrofluorocarbons have an ozone depletion coefficient of 0. By using these in combination, the effect of depleting the ozone layer is small, but the ozone depletion coefficient is not 0.
3. The amount of HCFC 141b used can be reduced, and it is also effective in solving the environmental problem of ozone layer depletion.

The fluorocarbon surfactant is preferably a surfactant containing a fluorine atom in its constituent molecule and having a fluoroalkyl group and a polyether group reactively bonded to each other. The fluoroalkyl group may be linear or branched. It can be a letter.

Further, as the perfluoroalkane used as the auxiliary foaming agent component, C5F12, C6F14,
And a mixture thereof and hydrofluorocarbon,
HFC134a or the like is applicable.

[0018]

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

Polyol A is an aromatic amine-based polyether polyol having a hydroxyl value of 460 mgKOH / g and catalyst A.
Is Kaoizer No. 1 manufactured by Kao Co., Ltd., and foam stabilizer A is a fluorocarbon surfactant F manufactured by Sumitomo 3M Co., Ltd.
C-170C, foam stabilizer B is a silicon-based surfactant F-335 manufactured by Shin-Etsu Chemical Co., Ltd., and foaming agent is HCFC123,
HCFC141b, C5F12, and HFC134a, which are mixed as a premix component by mixing the respective raw materials in a predetermined mixing number.

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

The premix component and the isocyanate component thus prepared and mixed are mixed and stirred in a predetermined mixing number, foamed by a high-pressure foaming machine, and filled inside a box consisting of an inner box and an outer box to form a heat-insulating box. Obtained. Regarding the physical properties of the raw material blending part and reactivity, foam thermal conductivity, foam cell diameter, foam density, and foam void property at this time (Table 1)
~ 8.

As an auxiliary foaming agent component, HFC134
When a was used, a static mixer was installed in a part of the premix circulation path of the high-pressure foaming machine, and HFC134a was dissolved from this part to prepare a premix component.

Also, as a comparative example, the same applies when a fluorocarbon-based surfactant and a silicone-based surfactant are used alone, or when the mixing mol% of the auxiliary foaming agent component exceeds the limit range. A from (Table 2)
Shown in I.

[0024]

[Table 1]

[0025]

[Table 2]

As described above, the foamed heat insulating material and the heat insulating box of the present invention, as the auxiliary foaming agent, are perfluoroalkane of 2 to 60 mol% of the total number of the foaming agent, or 10 of the total number of the foaming agent.
As long as a hydrofluorocarbon content of up to 40 mol% is used within this range, all of the foam properties such as heat insulation performance, foam density and foam void properties are excellent, and an excellent foam insulation material and insulation box suitable for refrigerators and freezers. You can get the body.

Although the details of the mechanism of cell miniaturization are unknown, the compatibility between the auxiliary foaming agent and the polyol component is poor, and as a result of emulsifying and dispersing as finely as possible in the premix, I think it will be possible.

As shown in Comparative Examples, when no perfluoroalkane and hydrofluorocarbon were used, HCFC123 and HC were used.
Due to the poor gas thermal conductivity of FC141b, the heat insulation performance of urethane foam is greatly deteriorated as compared with CFC11.

Further, 60 mol% of perfluoroalkane is used.
If used over the range, the foam density is greatly increased due to the poor foaming efficiency of the perfluoroalkane, and the gas thermal conductivity in the cell is gradually deteriorated, so that the effect of improving the heat insulating performance cannot be achieved.

When the hydrofluorocarbon is used in an amount of more than 40 mol%, the froth void becomes severe and the heat insulation performance is adversely affected, and the flowability of the foam is deteriorated to deteriorate the quality of the heat insulation box.

Further, when the fluorocarbon type surfactant and the silicon type surfactant are used alone, cell roughness occurs.

As described above, the foamed heat insulating material of the present invention can obtain a foamed heat insulating material having very fine cells even when HCFC123, HCFC141b, or a mixture thereof is used as a foaming agent component. By reducing the radiant heat conductivity, it is possible to obtain a foamed heat insulating material having heat insulation performance equivalent to that of conventional R11 foaming. Also,
By applying perfluoroalkanes and hydrofluorocarbons with an ozone depletion potential of 0, HCFC12
3, and since the amount of HCFC 141b used can be greatly reduced, it can greatly contribute to solving the environmental problem of ozone depletion more than ever before.

The heat insulating box filled with the foamed heat insulating material is extremely useful as a refrigerator and a freezer, and can secure excellent quality as a heat insulating box.

[0034]

As described above, according to the present invention, the organic polyisocyanate, the polyol, the catalyst, the mixture of the fluorocarbon type surfactant and the silicon type surfactant as the foam stabilizer, and the HCFC123 and HCFC141 as the foaming agent components.
b and the mixture thereof and 2 to 60 mol% of perfluoroalkane of the total number of foaming agents as an auxiliary foaming agent component are mixed and stirred to obtain a foamed heat insulating material formed by foaming.

The present invention further relates to an organic polyisocyanate,
Polyol, catalyst, mixture of fluorocarbon type surfactant and silicone type surfactant as foam stabilizer, HCFC123, HCFC141b as foaming agent component, and 10 to 4 of total number of foaming agent components as mixture and auxiliary foaming agent component.
This is a mixture of 0 mol% of hydrofluorocarbon and agitated to obtain a foamed heat insulating material formed by foaming.

Further, the foamed heat insulating material is foamed and filled in each of the spaces formed by the inner box and the outer box to obtain a heat-insulated box body.

Therefore, HCFC123 as a foaming agent component,
Since it is possible to obtain a foamed heat insulating material having extremely fine cells even when using HCFC141b or a mixture thereof, it is possible to obtain a foamed heat insulating material having a heat insulating performance equivalent to that of conventional R11 foaming. Can be done.

The foamed heat insulating material thus obtained is extremely useful as a foamed heat insulating material for electric refrigerators having a uniform fine cell structure due to uniform foaming behavior and being excellent in foam density, foam strength and void property. It is possible to provide various foam insulation materials.

Further, by filling the foamed heat insulating material to form a heat insulating box, the quality as an excellent heat insulating box can be secured without problems such as deterioration of heat insulating performance. It can greatly contribute to the solution of global environmental problems such as ozone depletion due to CFC.

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Claims (4)

[Claims] 1. An organic polyisocyanate, a polyol,
Catalyst, mixture of fluorocarbon type surfactant and silicone type surfactant as foam stabilizer, HC as blowing agent component
FC123, HCFC141b, and a mixture thereof and a perfluoroalkane of 2 to 60 mol% of the total blowing agent as an auxiliary blowing agent component are mixed and stirred, and a foamed heat insulating material produced by foaming. 2. An organic polyisocyanate, a polyol,
Catalyst, mixture of fluorocarbon type surfactant and silicone type surfactant as foam stabilizer, HC as blowing agent component
FC123, HCFC141b, and a mixture thereof and a foaming heat insulating material produced by foaming by mixing and agitating 10 to 40 mol% of hydrofluorocarbon of the total number of foaming agents as an auxiliary foaming agent component. 3. An insulating box body made of a foamed heat insulating material according to claim 1, wherein an outer box, an inner box, and a space formed by the outer box and the inner box are foam-filled. 4. A heat insulating box body made of a foamed heat insulating material according to claim 2, wherein an outer box, an inner box, and a space formed by the outer box and the inner box are foam-filled.