JPH0797470A - Thermal insulation foam and thermal insulation box - Google Patents

Abstract

PURPOSE:To obtain a thermal insulation foam excellent in thermal insulation properties, etc., without causing any environmental problems by mixing an org. polyisocyanate, a foam stabilizer, a catalyst, water, a polyether polyol, and a specific blowing agent and allowing the resulting mixture to foam. CONSTITUTION:A thermal insulation foam is obtd. by mixing an org. polyisocyanate (e.g. a polymeric MDI), a foam stabilizer (e.g. F-335, a product of Shin-Etsu Chemical Co., Ltd.), a catalyst (e.g. Kaolizer No. 1, a product of Kao Corp.), water, a polyether polyol (e.g. a mixture of an arom.-amine-based polyether polyol and an ethylenediamine-based polyether polyol), and a blowing agent comprising 70-60wt.% cyclopentane and 30-40wt.% at least one hydrocarbon selected from the group consisting of n-pentane, 2-methylbutane, and 2,2- dimethylpropane, and then by the resulting mixture to foam.

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, etc., 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 hydrochlorofluorocarbon (hereinafter referred to as HCFC) have been attracting attention. Is CF
Organic polyisocyanate for the purpose of reducing the amount of C used.
1,1-dichloro-2,2, a hydrochlorofluorocarbon that is a substitute for CFC and has little effect on ozone layer depletion, using a carbon dioxide gas obtained by the reaction of water with water as a part of the blowing agent. Various improvement efforts are being investigated, such as foaming with 1,2-trifluoroethane, 1,1-dichloro-1-fluoroethane, monochloro-difluoromethane, and 1-chloro-1,1-difluoroethane.

On the other hand, 1,1-difluoroethane, difluoromethane, and 1,1-difluoroethane, which are hydrofluorocarbons (hereinafter referred to as HFC), have no effect on ozone destruction.
Various improvements have been studied for foaming with 1,1-trifluoroethane, 1,1,1,2-tetrafluoroethane, or pentane, which is a hydrocarbon (hereinafter referred to as HC).

"Urethane International Forum 93" (1993
Sumitomo Bayer Urethane Co., Ltd. “P
In the announcement of "entane Blown Rigid Foam", it was stated that pentane was used as a foaming agent for urethane foam. Since pentane is non-polar, it is pointed out that it has poor compatibility with most polyether polyols. ing.

[0005]

Hydrocarbon is a substitute foaming agent for urethane foam, which is indispensable for global environment protection and has no effect on ozone layer depletion and has very little effect on global warming.

However, among the hydrocarbons, cyclopentane has poor compatibility with polyether polyol which is a general-purpose raw material for rigid urethane foam, and the number of cyclopentane added is limited.

In addition, the boiling point of cyclopentane is 49.3, which is 2 times that of CFC11, which is a conventionally used room temperature boiling foaming agent.
It is extremely high compared to 3.8 ° C and 32.0 ° C of HCFC141b. In order for cyclopentane to vaporize, reaction heat generated by urethane reaction, urea reaction, etc. is needed more than ever, and foam foaming efficiency is greatly reduced. To do.

Therefore, in the case of applying cyclopentane alone as the blowing agent component, in order to obtain the same foam density as in the conventional case, the carbon dioxide gas generated by the reaction between water and the organic polyisocyanate is increased by increasing the number of water addition parts. It had to be used as part.

Therefore, in the conventional method, the composition ratio in the bubbles of carbon dioxide having a large gas thermal conductivity is increased, and the increase in the gas thermal conductivity in the bubbles is unavoidable to deteriorate the foam thermal conductivity.

In view of the above-mentioned problems, the present invention has a main object of protecting the global environment, has no influence of ozone layer depletion, and has cyclopentane, which is one of the HCs having an extremely small influence on global warming, as a blowing agent. Even when used, it provides a high-quality foamed heat insulating material capable of improving foam fluidity and reducing foam density and foam thermal conductivity.

[0011]

In order to solve the above problems, the present invention provides an organic polyisocyanate, a foam stabilizer, a catalyst,
Water, polyether polyol, and cyclopentane as a blowing agent component and 30 to 40% by weight of the blowing agent component of normal pentane, or 2-methylbutane, or at least one or more components of 2,2-dimethylpropane are mixed and stirred,
Foam insulation produced by foaming.

Further, organic polyisocyanate, foam stabilizer,
A catalyst, water, a polyether polyol, and cyclopentane as a blowing agent component, and at least one component of 20 to 30% by weight of the blowing agent component of an aliphatic hydrocarbon having a boiling point of 0 degrees or less and a carbon number of 4 or more are mixed and stirred. , Foam insulation generated foam.

Further, the present invention is to provide an insulating box body comprising an outer box, an inner box, and the foamed heat insulating material foam-filled in a space formed by the outer box and the inner box.

Here, the aliphatic hydrocarbon having a boiling point of 0 ° C. or less and a carbon number of 4 or more is preferably n-butane having a boiling point of −0.5 ° C., 1-butene having a boiling point of −6.3 ° C., boiling point −11. 0.7 ° C
2-methylpropane, 2-methylpropene having a boiling point of -6.9 ° C, and the like.

[0015]

With the above constitution, 30-40% by weight of normal pentane of the blowing agent component, or 2%, of the blowing agent component can be obtained without increasing the number of parts of cyclopentane having low compatibility with polyol.
-Methylbutane or at least one or more components of 2,2-dimethylpropane by mixing and stirring,
Moreover, since the foaming agent component is mixed and stirred with at least one component of 20 to 30% by weight of a boiling point of 0 ° C. or less and an aliphatic hydrocarbon having 4 or more carbon atoms, the foaming efficiency of the urethane foam is greatly improved. , The foam density is significantly reduced.

Therefore, it becomes possible to reduce the amount of water added necessary to obtain the same foam density as in the conventional case, so that the composition ratio in bubbles of carbon dioxide gas generated by the reaction between water and the organic polyisocyanate is lowered, Since the composition ratio of hydrocarbon whose gas thermal conductivity is lower than that of carbon dioxide increases, the total gas thermal conductivity in the urethane foam bubbles decreases,
As a result, the foam insulation performance is improved.

Further, since it is not necessary to increase the number of added parts of cyclopentane having a large plasticizing action, it is possible to suppress the decrease in foam strength due to the swelling of cyclopentane in the urethane resin.

Therefore, a foaming agent of high quality which is excellent in foam heat insulation performance, foam density, foam strength, etc. is used by utilizing a foaming agent having an ozone depletion potential of 0 and a global warming potential which is extremely small and which is extremely effective against global environmental problems. The material can be provided.

[0019]

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

[Table 1] and (Table 2) show the raw material formulation of one example. Polyol is an aromatic amine-based polyester.
A mixture of terpolyol and ethylenediamine-based polyether polyol with a total hydroxyl value of 460 mgKOH / g, the catalyst is Kaoizer No. 1 manufactured by Kao Corporation, the foam stabilizer is F-335 manufactured by Shin-Etsu Chemical Co., Ltd., and the foaming agent is Cyclopentane, 2-methylbutane, n-pentane, n-butane, and 1-butene, which are mixed as a premix component by mixing the respective raw materials in a predetermined mixing ratio.

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

The premix component thus prepared and mixed and the isocyanate component are mixed and stirred 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. Got the body

As for the premix component, a foaming agent component and a mixed raw material of a polyether polyol and an auxiliary agent were mixed and prepared using a static mixer.

Free density of urethane foam at this time,
And, regarding the foam thermal conductivity of the panel foam foam cut out from the heat insulation box body that was foamed to aim at the core density of 34 kg / cm2 at the free density, and the state of the foam appearance such as floss voids and flyability (Table 1),
The results are shown in (Table 2) (Examples 1 to 8).

At the same time, as a comparative example, 2-methylbutane and n-pentane were added in a limited range of 30 to 40% by weight.
When the mixed foaming is carried out in excess of 10%, and when n-butane and 1-butene are mixed and foamed in an amount exceeding 20 to 30% by weight, which is a limited range, and when cyclopentane is solely foamed, the water addition amount is 2 levels ( The case of 0.5 parts and 2.0 parts is shown in (Table 1) and (Table 2), respectively (Comparative Example A to
J).

[0026]

[Table 1]

[0027]

[Table 2]

As described above, the foamed heat insulating material of the present invention is used as a foaming agent component when cyclopentane is mixed and foamed with 30 to 40% by weight of the foaming agent component 2-methylbutane and n-pentane. It was found that the foam Kf can be improved without changing the conventional foam density only in the case where 20 to 30% by weight of the blowing agent component, n-butane, and 1-butene were mixed and foamed in cyclopentane.

In addition, the foamed heat insulating agent produced by foaming cyclopentane as the foaming agent component in the above-mentioned limited range is not only foam Kf but also foam strength and foam appearance, Despite the use of hydrocarbons having a boiling point of 0 ° C. or less, high quality urethane foam free of froth voids due to bumping of the foaming agent can be obtained.

In the urethane foam produced by foaming by mixing 2-methylbutane, n-pentane, n-butane, and 1-butene beyond the limited range, foam density is increased, foam Kf is deteriorated, and froth voids are generated. It was difficult to apply the target quality because the target quality could not be achieved in any aspect.

As a result, the ozone depletion coefficient of 0, which is indispensable for protecting the global environment, and the hydrocarbon which has almost no effect on global warming, does not require a large prescription change.
A high-quality foam insulation material that can be easily applied as a foaming agent for urethane foam, and has excellent foam insulation performance, foam density, foam appearance, and a high-quality insulation box body that is foam-filled with the foam insulation material. It can be provided.

[0032]

As described above, according to the present invention, the organic polyisocyanate, foam stabilizer, catalyst, water, polyether polyol, cyclopentane as a foaming agent component and a foaming agent component are used.
A foamed heat insulating material produced by foaming by mixing and stirring 0 to 40% by weight of normal pentane, 2-methylbutane, or at least one component of 2,2-dimethylpropane.

Further, organic polyisocyanate, foam stabilizer,
A catalyst, water, a polyether polyol, and cyclopentane as a blowing agent component, and at least one component of 20 to 30% by weight of the blowing agent component of an aliphatic hydrocarbon having a boiling point of 0 degrees or less and a carbon number of 4 or more are mixed and stirred. , Foam insulation generated foam.

Further, the present invention is intended to obtain an insulating box body comprising an outer box, an inner box, and the foamed heat insulating material foam-filled in a space formed by the outer box and the inner box.

Therefore, it is possible to provide a high-quality foam insulation material having excellent foam insulation performance, foam density, foam strength, and the like, and a high-quality insulation box body in which the foam insulation material is foam-filled.

As a result, it becomes possible to easily apply a hydrocarbon, which has an ozone depletion coefficient of 0, which is indispensable for protecting the global environment, and has almost no influence on global warming, as a foaming agent for urethane foam.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area // (C08G 18/00 101: 00) C08L 75:04 (72) Inventor Hideo Nakamoto Osaka Prefecture 3-22, Takaidahondori, Higashiosaka-shi Matsushita Cold Machinery Co., Ltd.

Claims (4)

[Claims] 1. An organic polyisocyanate, a foam stabilizer, a catalyst,
Water, polyether polyol, and cyclopentane as a blowing agent component and 30 to 40% by weight of the blowing agent component of normal pentane, or 2-methylbutane, or at least one or more components of 2,2-dimethylpropane are mixed and stirred,
Foam insulation produced by foaming. 2. An organic polyisocyanate, a foam stabilizer, a catalyst,
Water, polyether polyol, and cyclopentane as a foaming agent component, and 20 to 30% by weight of the foaming agent component are mixed and stirred with at least one component of an aliphatic hydrocarbon having a boiling point of 0 degrees or less and a carbon number of 4 or more, Foam insulation produced by foaming. 3. An outer box, an inner box, an organic polyisocyanate foam-filled in a space formed by the outer box and the inner box, a foam stabilizer, a catalyst, water, a polyether polyol, and a foaming agent component. As cyclopentane and blowing agent component 3
A heat insulating box made of a foamed heat insulating material produced by foaming by mixing and stirring 0 to 40% by weight of normal pentane, 2-methylbutane, or at least one component of 2,2-dimethylpropane. 4. An outer box, an inner box, an organic polyisocyanate foam-filled in a space formed by the outer box and the inner box, a foam stabilizer, a catalyst, water, a polyether polyol, and a foaming agent component. Of cyclopentane and blowing agent
A heat insulating box made of a foamed heat insulating material produced by foaming by mixing and stirring 0 to 30% by weight of at least one component of an aliphatic hydrocarbon having a boiling point of 0 degrees or less and a carbon number of 4 or more.