JPH08169976A - Heat-insulating resin foam and its production - Google Patents

Abstract

PURPOSE: To provide a heat-insulating resin foam having excellent heat insulation properties and being highly safe from burning, explosion, etc., by using a new blowing agent having a low thermal conductivity and the possibility of environmental disruption such as an ozone depletion coefficient and a global warming count. CONSTITUTION: This foam is composed of closed cells and contains a blowing agent comprising at least one compound selected from the group consisting of a fluoroiodohydrocarbon, a perfluoroalkene and a hydrogen-containing fluoromorpholine derivative in the closed cells. This foam is produced by foaming and molding a resin composition containing the above blowing agent, a polyol, a polyisocyanate, an urethane formation catalyst and a foam stabilizer under mixing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat insulating resin foam used for a refrigerator, a freezer or a heat insulating material for construction, and a method for producing a heat insulating resin foam using a novel foaming agent.

[0002]

2. Description of the Related Art In recent years, it has become a social problem that chlorofluorocarbon has a great influence on ozone layer depletion. It has been decided to abolish it. Therefore, 1,1-dichloro-1-, which is a substance with a low ozone depletion potential (ODP)
Fluoroethane (HCFC-141b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-1
23) and the like are used as a foaming agent and are put to practical use in refrigerators and the like. However, HCFC-141b, HCFC12
No. 3 has a chloro group in its molecular structure and its ozone depletion potential is not zero. For this reason, they are transient alternatives and need to be replaced by substances that can be used in the long term.

Hydrocarbons such as cyclopentane do not contain a halogen element as a foaming agent that can be used for a long period of time, and therefore do not destroy the ozone layer. It has been announced that it is a compound having both properties (5 May 1993).
Monthly Polyurethanes International Forum 93 Proceedings 197
Page, "Pentane foaming rigid urethane foam" by Gerhard Heilich and Yoshinori Kihara). It is also disclosed that its flammability can be solved by safety measures in manufacturing technology and by increasing the amount of flame retardant in the foam. However, the polyurethane foam using pentane as the blowing agent is
Compared with polyurethane foams using conventional foaming agents such as 141b and HCFC123, there is a problem that the heat insulation is poor and the safety against combustion and explosion is low.

On the other hand, fluorocarbons that do not contain chlorine at all have been attracting attention as a similar CFC substitute foaming agent. In EPA351614 (Japanese Patent Laid-Open No. 2-86635), perfluorohexane, which is a fully-fluorinated substance, is used as a foaming agent. The form etc. used as are reported. The thermal conductivity of a heat-insulating body composed of a foam having small bubbles in which the convection of the gas in the bubbles is negligible depends on the heat conduction by the gas present in the bubbles and the heat radiation in the bubbles. It is represented by the sum of heat conduction and solid heat conduction of the resin part. Therefore, when a perfluorinated compound such as the above-mentioned perfluorocarbons is used as a foaming agent, the bubble diameter is reduced to reduce the radiation component, and the density is reduced to reduce the contribution of solid heat conduction in the resin portion. It is important to.

Regarding the cell diameter, the cells are usually made finer by introducing a foaming nucleus (for example, Japanese Patent Application Laid-Open No. 3-54231). Perfluoroalkane such as perfluoropentane is used as the foaming core. By using a perfluoroalkane as an emulsifier to emulsify the polyol composition and further combining it with a foaming nucleating agent such as silica gel or starch, it is possible to obtain an effect of making bubbles finer. Also, as a foaming agent, HCF
There is also a proposal to obtain a polyurethane having a low thermal conductivity by making an emulsion in which 5.5% or less of perfluorocarbon is added together with C123 and HCFC141b as a cell nucleus to miniaturize the cells (JP-A-5-186629). Gazette).

However, from the viewpoint of environmental destruction due to CFCs such as ozone layer depletion or global warming, perfluoroalkanes such as perfluoropentane also have a longer life in the atmosphere than specified CFCs, and their lifespan is longer. It is estimated to be over 500 years old and its use is about to be restricted. Further, as a method for producing a heat insulating resin foam using a fluorinated alkene as a foaming agent, a method in which perfluoro-2-pentene is used in combination with hydrocarbon (Japanese Patent Laid-Open No. 5-2472).
49) or a method of using perfluoroalkylethylene in combination with water (JP-A-5-279653). On the other hand, as a method of integrally molding a resin foam, there is a method of adjusting the physical properties of the foam by adding water.
A characteristic of foaming by adding water is that the heat of reaction is generated by the reaction between isocyanate and water, and carbon dioxide is also generated to enhance the foamability. It should be noted that the urea-bonded resin component formed by the reaction of isocyanate and water is more robust than the urethane bond and can impart flame retardancy. This method
It was very effective when used as a substitute for conventional CFCs. However, carbon dioxide is contained in the resin foam,
Since the gas thermal conductivity is increased, even if a foaming agent having a low thermal conductivity is used, its performance is not fully utilized. There is a demand for a technique that utilizes a method of adding water and absorbs carbon dioxide after foam formation to improve heat insulation. As the technique, it has been proposed to add sodium hydroxide or soda lime as a carbon dioxide reactive reagent to absorb carbon dioxide and improve the heat insulating property (Japanese Patent Laid-Open No. 6-322166).

[0007]

The present invention has low thermal conductivity, ozone depletion potential (ODP), and global warming potential (G).
It is intended to provide a heat insulating resin foam having excellent heat insulating properties and safety such as flammability and explosive properties by using a new foaming agent having almost no environmental damage such as WP). . Moreover, this invention aims at providing the manufacturing method of the heat insulation resin foam which uses a novel foaming agent.

[0008]

According to the present invention, at least one compound selected from the group consisting of fluorinated iodohydrocarbons, perfluoroalkenes and hydrogen-containing fluorinated morpholine derivatives is used as a foaming agent. Characterize. The heat insulating resin foam of the present invention is composed of a foamed resin composition having closed cells, and the closed cells contain the gas of the foaming agent.

The method for producing a heat insulating resin foam of the present invention is a foam comprising at least one compound selected from the group consisting of fluorinated iodohydrocarbons, perfluoroalkenes and hydrogen-containing fluorinated morpholine derivatives. Agent,
The resin raw material composition containing a polyol, a polyisocyanate, a urethane reaction catalyst and a foam stabilizer is mixed to foam and mold to obtain a heat insulating resin foam.

In this case, the blowing agent is preferably a mixture of a fluorinated iodohydrocarbon and a perfluoroalkene and a hydrogen-containing fluorinated morpholine derivative. Another preferable foaming agent of the present invention is a mixture of the above-mentioned foaming agent with a hydrocarbon, particularly a hydrocarbon having a boiling point of 50 ° C. or lower. In another preferred embodiment, water is further used as a foaming agent in addition to the above-mentioned foaming agent.

Polystyrene and phenol resins can be used as the resin for forming the heat insulating resin foam of the present invention, but polyurethane is particularly preferable from the viewpoint of controlling the bubble diameter and facilitating on-site foaming. Therefore, hereinafter, the resin foam using the urethane reaction will be described. In the present invention, the blowing agent is particularly preferably used in combination with a fluorinated iodohydrocarbon, and another blowing agent. When this fluorinated iodohydrocarbon is used, it has a boiling point of 1 in the resin composition raw material.
It is preferable to add at least one of an organic carbonate compound, an ester, and an epoxide at 00 ° C. or higher.

It is also effective to add a reducing agent or an oxygen absorbent to the resin raw material composition. The reducing agent is dispersed in a polyisocyanate composition together with a surfactant to form a polyisocyanate emulsion, which is
It is preferable to form a resin raw material composition by mixing A preferred reducing agent is an aqueous solution of sodium thiosulfate. When a fluorinated iodohydrocarbon is used as a foaming agent, the polyol preferably contains at least 30 wt% of a non-amine-based polyol.

In one embodiment of the present invention, the resin raw material composition is obtained by mixing a polyisocyanate composition mixed with a fluorinated iodohydrocarbon and a premix containing a polyol, a urethane reaction catalyst, and a foam stabilizer. It is prepared by In another embodiment, the resin raw material composition contains, as a foaming nucleus, a salt soluble in a primary alcohol or a secondary alcohol having 3 or less carbon atoms. In another aspect of the present invention, a method for producing a heat insulating resin foam is a complex compound of a fluorinated iodohydrocarbon and a non-conjugated bond amine, ammonium salt or quaternary ammonium salt, a polyol, and a polyisocyanate. A step of foaming and molding by mixing a resin composition raw material containing the fluorinated iodocarbon is separated from the complex compound by the heat of reaction between the polyol and the polyisocyanate. Hydrogen acts as a blowing agent. In the above aspect, the resin composition raw material,
Furthermore, it is preferable that at least one selected from the group consisting of an organic tin compound, a metal salt of an organic acid, an aromatic amine, and an organic phosphorus compound is contained as a urethane reaction catalyst. Further, in the above aspect, the resin composition raw material is further in a range up to an equimolar amount with the complex compound,
Further, it is preferable to contain 10 parts by weight or less of water with respect to 100 parts by weight of the polyol component.

In a preferred embodiment of the method for producing a heat insulating resin foam containing water as a foaming agent, the resin raw material composition contains an epoxide and a carbon dioxide fixing catalyst, and carbon dioxide produced during the foaming step is the epoxide. And a carbonate compound to form a carbonate compound, thereby reducing the pressure inside the bubbles of the resulting foam. In the above aspect, the resin raw material composition is a premix containing a polyisocyanate composition in which a fluorinated iodohydrocarbon and a carbon dioxide-immobilized catalyst are mixed, a polyol, a urethane reaction catalyst, an epoxide, and a foam stabilizer. It is preferably formed by mixing with. Further, in the above aspect, the resin raw material composition contains a complex compound of a carbon dioxide-immobilized catalyst and a fluorinated iodohydrocarbon, and the complex compound is decomposed by the heat of reaction between the polyol and the polyisocyanate to produce fluorine. It is preferable that the method includes a step of producing a fluorinated iodohydrocarbon and a carbon dioxide-immobilized catalyst, and the produced carbon dioxide-immobilized catalyst acts on the reaction between the epoxide and the carbon dioxide produced during the foaming step.

The hydrocarbon used as the blowing agent together with the fluorinated iodohydrocarbon is preferably at least one selected from the group consisting of pentane, isopentane and cyclopentane. The preferable mixing ratio of this hydrocarbon is 45 to 96 mol%. As the foam stabilizer, it is preferable to use both a dimethylsiloxane-oxyalkylene copolymer and a dimethylsiloxane-oxyalkylene copolymer having a fluoroalkyl group in the molecule.
Of the materials added to the resin raw material described above, the reducing agent and the carbon dioxide-immobilized catalyst are preferably mixed with the isocyanate composition. Other materials are preferably mixed into the polyol composition.

Since both of the novel blowing agents used in the present invention have a relatively short life in the atmosphere, they have little or no global warming potential. Fluorinated iodohydrocarbons have a much shorter life in the atmosphere than conventional CFCs because iodine is likely to dissociate from the molecule when irradiated with ultraviolet rays. Further, perfluoroalkene is expected to have a short life because the reaction of OH radicals to the double bond portion easily proceeds in the atmosphere. The hydrogen-containing fluorinated morpholine derivative has a carbon-hydrogen bond more than perfluoromorpholine and perfluoromethylmorpholine, which are fluorinated morpholine derivatives, because hydrogen in the molecule is near oxygen and nitrogen. Due to its weak energy and easy decomposition, its lifetime in the atmosphere is expected to be short.

Further, both of these substances have low gas thermal conductivity, and the resin foam using them has no environmental load and is an excellent heat insulating material from the viewpoint of heat insulating property. further,
These foaming agents are nonflammable and are advantageous materials in terms of safety. In particular, fluorinated iodohydrocarbons have the lowest thermal conductivity among them and have a short life in the atmosphere.
Furthermore, since it has iodine, it has a negative catalytic effect on combustion and can impart flame retardancy and self-extinguishing properties to the foamed resin composition. When a flammable ether or hydrocarbon is used together as the foaming agent, the mixed foaming agent itself can be made incombustible. Fluorinated iodohydrocarbons are not only non-combustible, but also release iodine upon ignition to act as a fire extinguisher. It also acts as a non-flammable and self-extinguishing foaming agent.

At present, a hydrocarbon-based foaming agent is one of the ones attracting attention as a foaming agent having no environmental load. As the hydrocarbon, pentane, isopentane, cyclopentane and the like are useful as a foaming agent having a high heat insulating property. But,
Hydrocarbons are generally flammable and therefore dangerous.
When one of the fluorinated iodohydrocarbons, perfluoroalkenes, and hydrogen-containing fluorinated morpholine derivatives of the present invention is mixed with the hydrocarbon blowing agent, the resulting resin foam becomes flame-retardant. Therefore, this resin foam is effective not only as a refrigerator but also as a heat insulating material for building materials. The mixing ratio of the fluorinated iodohydrocarbon, the perfluoroalkene and the hydrogen-containing fluorinated morpholine derivative to the hydrocarbon blowing agent is 4 mol% or more and 55 mol% or more.
Within the following ranges, the mixed foaming agent loses gas flammability or explosiveness. Further, in particular, fluorinated iodohydrocarbon has not only flame retardancy but also self-extinguishing property. Therefore, when it is added to the hydrocarbon foaming agent within the above range, not only flame retardancy but also self-extinguishing property can be imparted. Among them, compounds such as trifluoroiodomethane having a boiling point of 0 ° C. or lower can be used as a refrigerant having no environmental load and have self-extinguishing property, so that there is no fear of fire. That is,
When hydrocarbons are used as a refrigerant, even if they are mixed in the refrigerant, the effect of the refrigerant is not impaired and it can be made incombustible. The constitution which maximizes the effect of the fluorinated iodohydrocarbon is the main object of the present invention.

Fluorinated iodohydrocarbons are very soluble in the resin raw material, but when used alone as a foaming agent, the polyol premix and polyisocyanate containing this foaming agent are used. The reaction with is much slower than when using a conventional freon blowing agent. Therefore, the bubble diameter of the obtained polyurethane foam tends to increase. On the other hand, perfluoroalkene and hydrogen-containing morpholine fluoride derivative are difficult to dissolve in polyol and form an emulsion. Since the fine particles such as perfluoroalkene dispersed in the polyol act as a bubble nucleus during foaming, the obtained polyurethane foam has a small bubble diameter. However, the formation of the emulsion increases the viscosity of the polyol premix and reduces the mixability of the raw materials. Therefore, the density of the obtained resin foam tends to be high, or the foaming tends to occur easily.

Surprisingly, the present inventors have shown that by using an iodinated fluorohydrocarbon in combination with a perfluoroalkene or a hydrogen-containing fluorinated morpholine derivative as a blowing agent, a hybrid effect is exhibited, and each compound is used. It has been found that a polyurethane foam with better thermal insulation is obtained than when used separately as blowing agents. This is considered as follows. That is, when these two foaming agents are used in combination, the polyol composition forms an emulsion by mixing the perfluoroalkene or the hydrogen-containing fluorinated morpholine derivative, but is fluorinated with excellent compatibility with the polyol. By adding iodohydrocarbon, the viscosity of the emulsion is lowered, and the emulsion is uniformly mixed in a short time to improve the foamability. As a result, a polyurethane foam having a relatively small bubble diameter, a low resin density, and no bubble breakage can be obtained.

It is also a very effective means to add water together with the above-mentioned foaming agent and use carbon dioxide produced by the reaction of water and isocyanate as the foaming agent. When the blowing agent of the present invention is used in combination with water, for example, a combination of fluorinated iodohydrocarbon and water produces a high heat of reaction during mixed foaming, so that the fluorinated iodohydrocarbon having good compatibility with the polyol can be obtained. Since the amount of heat required for vaporization and foaming is supplied, the foamability can be improved. In addition, foaming with water has an effect of making bubbles finer, and is effective in improving the feature that the bubble shape of the fluorinated iodohydrocarbon tends to be large. Furthermore, the following effects are brought about. That is, the gas of the foaming agent having a good compatibility with the resin raw material such as polyol is easily permeated from the resin foam over time. However, since the water-foamed resin composition has a high cross-linking density, it becomes difficult for the foaming agent gas to permeate,
Stable heat insulation performance over time. Water foaming is also effective for perfluoroalkene and hydrogen-containing fluorinated morpholine derivatives because it improves the foamability.

Further, it is effective to add an organic carbonate compound, an ester or an epoxide having a boiling point of 100 ° C. or higher to the resin raw material because the foamability is improved. Fluorinated iodohydrocarbons are generally fluorine compounds but have the property of being easily compatible with resin raw materials such as polyols. Since the compatibility is high, bubbles tend to become large in the foaming process, which deteriorates the heat insulating performance of the obtained foam. Therefore, by mixing polar inactive hydrogen-containing compounds such as carbonate, ester, and epoxide, and by the dilution effect,
Foamability and cell size can be adjusted. Further, when the above compound has poor compatibility with the polyol, the viscosity of the premix emulsion is lowered, whereby the foamability and the cell diameter can be adjusted. Therefore, it is preferable that the perfluoroalkene and the hydrogen-containing fluorinated morpholine derivative are effective even when used as a foaming agent.

The novel foaming agent of the present invention has an advantage that it has no or very small load on the environment because it has a short life. There is concern that performance may deteriorate. Therefore, it is preferable to take measures to prevent such inconvenience. One is to add a reducing agent to the resin. The reducing agent reduces oxidative substances such as iodine generated by decomposition of iodinated fluorohydrocarbons and the like, and keeps the heat insulating performance of the foam stable for a long period of time. Further, the addition of the oxygen absorbent is effective for stabilizing the iodinated fluorohydrocarbon in the bubbles of the heat insulating resin foam. This is because the oxygen absorbent reduces the amount of oxygen dissolved in the bubbles and suppresses the oxidation of iodinated fluorohydrocarbon. When the oxygen absorbent is mixed with polyisocyanate, which has the same property as an electron acceptor, a stable dispersion liquid can be obtained.

When a fluorinated iodohydrocarbon is used as a blowing agent, it is preferable to use a polyol composition containing a non-amine polyol. The amine and the fluorinated iodohydrocarbon form a complex compound, which does not easily foam and the foaming property deteriorates. In order to avoid this, it is necessary to reduce the amine component in the resin raw material. A polyol containing at least 30 wt% of a non-amine-based polyol does not easily form a complex compound with a fluorinated iodohydrocarbon, and the disadvantage due to the formation of the complex compound is eliminated.

In one preferred embodiment of the invention,
A heat insulating resin foam is manufactured by mixing and foaming a resin raw material containing a complex compound of a fluorinated iodohydrocarbon and an amine or ammonium salt having a non-conjugated bond, or a quaternary ammonium salt. The fluorinated iodohydrocarbon easily forms and stabilizes a complex compound with the amine or ammonium salt. The present inventors have found that this complex compound is very effective in producing a heat insulating resin foam and improving performance. Preferred complex compounds used here are as follows. That is, although the binding force greatly differs depending on the compound, it is in a solid or liquid state at room temperature, does not easily vaporize at the boiling point of the fluorinated iodohydrocarbon used, and does not separate even when left standing. However, depending on the bonding force, the fluorinated iodohydrocarbon is separated upon heating and liberated. When water is added to the complex compound, it is separated into an upper layer and a lower layer, the upper layer is a water layer and a liquid in which amine is dissolved, and the lower layer is a liquid layer made of fluorinated iodohydrocarbon. When fluorinated iodohydrocarbons are exposed to light, iodine is immediately separated and colored red. However, complex compounds with amines are extremely stable to light and do not decompose at all. Such a complex compound acts as a foaming agent and as a urethane reaction catalyst. The examples show the effects of various complex compounds.

In the present invention, it is preferable to add the complex compound as a composition containing the complex compound in a solid state or in a high boiling point liquid state in which the weight does not change at room temperature for one week or more. This can prevent photodecomposition of the fluorinated iodohydrocarbon and reduce the loss of the fluorinated iodohydrocarbon during foaming. Depending on the binding force of the complex compound, it becomes a solid or high boiling point liquid state, so volatility can be suppressed, storage stability of the pre-foaming raw material can be improved, and loss of the foaming agent and deterioration of the premix during operation can be suppressed. be able to.

The resin foam according to one embodiment of the present invention contains carbon dioxide and a foaming agent selected from the group consisting of fluorinated carbon iodide, perfluoroalkene and hydrogen-containing fluorinated morpholine derivative in closed cells. There is. further,
In a preferred embodiment, the epoxide mixed in the resin raw material stage contains a carbonate component in which carbon dioxide is immobilized in the presence of a carbon dioxide immobilization catalyst. The carbon dioxide-immobilized catalyst is preferably a catalyst containing a nucleophile and / or an electrophile. In this configuration, carbon dioxide generated in the foaming process is absorbed and immobilized,
Carbon dioxide, which has a high thermal conductivity, does not contribute to the gas thermal conductivity of the resin foam. Therefore, it is possible to exhibit excellent thermal conductivity characteristics of the foaming agent. According to the present invention, a resin foam having a high heat insulating property can be obtained due to the low gas thermal conductivity of the foaming agent.

When water is added to the raw material premix, carbon dioxide is released by the reaction based on Chemical formula 1 or the bond between the isocyanates shown in Chemical formula 2 and acts as a foaming agent.

[0029]

Embedded image

[0030]

Embedded image

These reactions were indispensable for the purpose of improving the foamability, making the cells finer, and increasing the foam strength, but the thermal conductivity of the gas in the bubbles increased due to the release of carbon dioxide. Was a problem. As shown in Chemical formula 3, a carbonate compound is produced by the reaction between carbon dioxide and an epoxide. This carbonate compound has an effect of improving foamability and an effect as a plasticizer, and is a good substance for improving the heat insulating performance of the foam. Further, in the foaming process, the epoxide is polymerized to increase the strength as a resin component of the foam, which is preferable.

[0032]

Embedded image

Further, in the reaction of carbon dioxide and epoxide, it is preferable to use a catalyst containing a nucleophile and / or an electrophile as a carbon dioxide fixing catalyst because the reaction yield of the formula 3 is increased. However, before fixing carbon dioxide, the epoxide may undergo ring-opening addition polymerization with the resin raw material isocyanate or polyol, and depending on the composition, the epoxide may be lost. Further, since this carbon dioxide-immobilized catalyst also has a function of polymerizing isocyanate, it cannot be mixed with the polyisocyanate composition. However, since the fluorinated iodohydrocarbon and the carbon dioxide-immobilized catalyst are stabilized by the interaction, they can be added to the isocyanate composition and separated from the epoxide. This makes it possible to reduce the amount of epoxide used for polymerization and to form a heat-insulating resin foam having good performance without inhibiting the resin reaction.

Further, the composition in which a complex compound of a non-conjugated amine or ammonium salt or quaternary ammonium salt and a fluorinated iodohydrocarbon is mixed with a resin raw material together with an epoxide and a carbon dioxide fixing catalyst is also described above. Is a way to solve the problem. This promotes carbon dioxide immobilization, improves the immobilization rate, and lowers the gas thermal conductivity, so that a resin foam having a high heat insulating property can be formed. That is, the complex compound not only acts as a blowing agent by fluorinated iodohydrocarbons generated by decomposition with heat, but also does not have a catalytic action for carbon dioxide immobilization as a complex compound. It does not act as a carbon dioxide immobilization catalyst until it undergoes a decomposition process. As a result, the urethane reaction proceeds in a completely different dimension from the carbon dioxide fixing reaction. Then, since the carbon dioxide immobilization reaction occurs almost after the resin foam is formed, a strong resin foam can be formed, and the shape does not change even when the pressure is reduced. When a complex compound of a tertiary amine having no halogen ion and a fluorinated iodohydrocarbon is used, this complex compound can serve as a carbon dioxide-immobilized catalyst.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION The heat insulating resin foam and the method for producing the same according to the present invention will be described in more detail below.
The novel blowing agent used in the present invention is selected from the group consisting of fluorinated iodohydrocarbons, perfluoroalkenes and hydrogen-containing fluorinated morpholine derivatives. This foaming agent
In the resin raw material and the manufacturing method that have been used conventionally, it exerts sufficient performance as a blowing agent. The fluorinated iodohydrocarbon as the foaming agent is preferably a compound having 4 or less carbon atoms and a boiling point of 65 ° C or less. Examples of such fluorinated iodohydrocarbons include iodotrifluoromethane (chemical formula CF ₃ I: boiling point-22.5 ° C.) (the chemical formula and boiling point are shown in parentheses; the same applies hereinafter), iodopentafluoroethane ( CF ₃ CF ₂ I: 12 to 13 ° C.) 1-iodoheptafluoropropane (CF ₃ CF ₂ CF ₂ I: 3)
9 ° C) 2-iodoheptafluoropropane (CF ₃
CFICF ₃ : 39 ° C), iodo-1, 1, 2, 2-
Tetrafluoroethane (C ₂ HF ₄ I: 41 ° C.), 2-iodo-1,1,1-trifluoroethane (C ₂ H ₂ F ₃
I: 55 ° C.), iodotrifluoroethylene (C ₂ F ₃
I: 30 ° C.), 1-iodo-1,1,2,3,3,3
- hexafluoropropane _{(CF 3 CHFCF 2 I),} 2
- Eye odo nonafluorobutyl -t- butane ((CF _{3) 3} C
I: 61 ° C.).

Perfluoroalkenes useful as blowing agents are dimers of hexafluoropropene, such as perfluoro-4-methyl-2-pentene, perfluoro-2-methyl-2-pentene and their derivatives. There is a mixed composition, which has a boiling point of 48-51.
It has a molecular weight of 300.04 at a temperature of 300.degree. C. and is composed of total fluorocarbon containing one carbon-carbon unsaturated bond in the molecule. In addition to hexafluoropropene dimer, perfluoro-2
A compound selected from -pentene, (perfluorobutyl) ethylene, (perfluoropropyl) ethylene, and octafluorocyclopentane is preferable because it has a proper boiling point as a foaming agent. Hydrogen-containing fluorinated morpholine derivatives useful as effervescent agents are, for example, either monohydroperfluoromorpholine or monohydroperfluoromethylmorpholine, or mixtures thereof. As monohydroperfluoromorpholine, there are 3H-octafluoromorpholine (molecular weight 231) and 2H-octafluoromorpholine (molecular weight 231), and the boiling point of perfluoromorpholine is 34.5 ° C. Therefore, it is estimated to be 30 to 40 ° C. As monohydroperfluoromethylmorpholine, octafluoro-4-difluoromethyl-morpholine (molecular weight 281, boiling point 66 to 67) is used.
C.) 3H-heptafluoro-4-trifluoromethyl-morpholine (molecular weight 281, boiling point 63.5-64.
5 ° C.), 2H-heptafluoro-4-trifluoromethyl-morpholine (molecular weight 281, boiling point 70 ° C. or lower), which have a boiling point of 70 ° C. or lower and have good foamability as a foaming agent for urethane foam. Is. Further, it is possible to mix each foaming agent. In particular, the configuration in which the fluorinated iodohydrocarbon is mixed with another perfluoroalkene or a hydrogen-containing fluorinated morpholine derivative, the bubble shape of the resin foam is miniaturized by the hybrid effect,
Further, self-extinguishing property can be imparted.

The above-mentioned foaming agent of the present invention is used by mixing with the following ketones, ethers, esters or hydrocarbons to improve the physical properties of the foam such as the strength and heat insulation performance of the resin foam. Can be improved. These compounds such as ketones contribute to the improvement of the physical properties of the foam by modifying the compatibility of the foaming agent with the resin raw material, optimizing the viscosity of the resin raw material, and lowering the boiling point by forming an azeotropic mixture with the foaming agent. To do. Examples of the ketone applied to the present invention include acetone (molecular weight 58.08, boiling point 56 ° C.), 2-butanone (molecular weight 72.1, boiling point 80).
℃) etc. Further, as the ether applied to the present invention, for example, furan (molecular weight 68.1, boiling point 32
℃) 2-methylfuran (molecular weight 82.1, boiling point 63 ~
66 ° C.), tetrahydrofuran (molecular weight 72.1, boiling point 66 ° C.), 2-methyltetrahydrofuran (molecular weight 86.1, boiling point 78 to 80 ° C.), 1,3-dioxolane (molecular weight 74.1, boiling point 74 to 75 ° C.), 2,5-dihydrofuran (molecular weight 70.1, boiling point 66 to 67 ° C.) and the like.

Examples of the ester applicable to the present invention include methyl acetate (molecular weight: 74.1, boiling point: 57.5).
° C), ethyl acetate (molecular weight 88.1, boiling point 76.5-7)
7.5 ° C), methyl formate (molecular weight 60.1, boiling point 34
° C), ethyl formate (molecular weight 74.1, boiling point 52-54
℃) etc. Hydrocarbons applicable to the present invention include:
For example, cyclopentane (molecular weight 70.2, boiling point 49.
3 ° C), isopentane (molecular weight 72.2, boiling point 28)
C.), normal pentane (molecular weight 72.2, boiling point 36.
1 ° C), 3-methylpentane (molecular weight 86.2, boiling point 6)
4 ° C.), cyclohexane (molecular weight 84.2, boiling point 80.
7 ° C, neohexane (molecular weight 86.2, boiling point 49 °
C), isohexane (molecular weight 86.2, boiling point 63.3
C.), normal hexane (molecular weight 86.2, boiling point 69.
7 ° C) and so on. In particular, cyclopentane, isopentane, and normal pentane have low thermal conductivity, and independently function sufficiently as a foaming agent, but by mixing with the above-mentioned foaming agent of the present invention, the heat insulating performance of the foam can be improved. . Further, these hydrocarbons are flammable and explosive, and therefore are dangerous to handle, but when combined with the foaming agent of the present invention, the flammability of the hydrocarbon is lowered, and the flame retardancy and self-extinguishing properties are reduced. There are advantages.

It is also preferred to use water as the blowing agent. When water is used as the foaming agent, it is possible to improve the foamability of the foaming agent of the present invention, and thereby, a resin foam having fine cells and low density can be formed. Since the effect of the mixed foaming agent described above varies depending on the raw material composition of the polyol, the catalyst, the foam stabilizer, etc., it is necessary to appropriately select the type and the addition amount of the foaming agent for mixing. Examples of the reducing agent added when the foaming agent of the present invention is used include silicic acid, phosphorous acid, boric acid, carbonic acid, thioacids such as metal salts of thiosulfate. In particular, sodium thiosulfate is the preferred reducing agent. Since these also act as bubble nuclei, it is preferable to add them as finely crushed micron-order fine particles. Also, it is dissolved in the raw material,
It is preferably precipitated during the foaming reaction and contained in the resin foam in a fine powder state. These fine powders are preferably added together with a surfactant, do not aggregate with each other, and do not lose reducibility in the raw material. The surfactant is most preferably a silicone foam stabilizer added to the resin raw material, and may be any commonly used anionic, cationic or nonionic surfactant. The reducing agent is preferably dispersed in the polyisocyanate together with the surfactant. This reducing agent
It acts to prevent the oxidizing substances produced by the decomposition of the foaming agent from adversely affecting the resin. Further, the reducing agent acts as a bubble nucleus of the foaming agent because it is mixed in the raw material as a fine powder or is precipitated during the foaming process.
Surfactants are necessary to obtain a stable dispersion form of the powder.

In the preferred production method of the present invention containing the reducing agent, water in which sodium thiosulfate is dissolved or alcohol or water in which an organic salt is dissolved is added to a polyisocyanate together with a surfactant. Disperse into an emulsion. And this emulsion,
A polyurethane foam is produced by mixing with a polyol composition containing a foaming agent and foaming. At this time, the water or alcohol particles in the emulsion act as bubble nuclei, and when the emulsion starts to disintegrate due to the heat generated by mixing the polyol and polyisocyanate, the water or alcohol reacts with the polyisocyanate. Therefore, sodium thiosulfate or an organic salt dissolved in water or alcohol is deposited, which also acts as a bubble nucleus. This further reduces the bubbles in the resulting foam.

Further, the foaming agent of the present invention is easily decomposed, for example, fluorinated iodohydrocarbon, and is partially decomposed during the resin formation reaction to liberate iodine, which deteriorates the resin or causes metal contact with the resin. There is concern that it may cause corrosion. However, iodine reacts with sodium thiosulfate uniformly dispersed in the resin to be reduced and becomes harmless.

By the way, when the resin is foamed using the fluorinated iodohydrocarbon as the foaming agent, the reaction between the polyol and the polyisocyanate is delayed, and compared with the case where other foaming agents are used. The bubble diameter becomes large. Therefore, when the fluorinated iodohydrocarbon is used as a part of the foaming agent, it is particularly preferable to use the polyol composition containing the alcohol and the salt dissolved therein. At this time, in addition to the salt acting as a bubble nucleus, the resin reaction is accelerated by the reaction of the alcohol with the polyisocyanate, and as a result, the bubble diameter of the obtained polyurethane foam becomes small. This effect becomes more remarkable as compared with the case of using a normal foaming agent.

Further, in the production method of the present invention, a salt soluble in a primary or secondary alcohol having a carbon number of 3 or less may be included in the raw material, and these salts may act as foam nuclei. it can. Examples of primary or secondary alcohols having 3 or less carbon atoms added to the polyol include monohydric alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, allyl alcohol, and divalent alcohol. Examples of the glycol include ethylene glycol, 1,3-propanediol, and trivalent alcohol such as glycerin. Further, as the above-mentioned salt, any salt which can be dissolved in the above alcohol in an amount of about 5 to 10% by weight or more can be suitably used regardless of whether it is an organic salt or an inorganic salt. For example, for methyl alcohol, calcium iodide, sodium iodide, lithium chloride, lithium iodide, potassium iodide,
Strontium bromide, barium bromide, calcium bromide, sodium bromide, calcium nitrate, magnesium nitrate, copper chloride, magnesium iodide, nickel bromide, potassium benzoate, lithium benzoate, zinc benzoate, ammonium benzoate, olein Ammonium acid, lithium acetate, potassium acetate, potassium propionate, potassium butyrate, sodium butyrate and the like can be used. Also,
For ethyl alcohol, potassium chloride, potassium iodide, sodium iodide, sodium thiocyanate,
Strontium bromide, sodium bromide, barium iodide, calcium bromide, calcium nitrate, copper chloride, ferric chloride, lithium bromide, magnesium iodide, ammonium bromide and the like can be used. Further, for propyl alcohol, lithium iodide, sodium iodide, calcium bromide, copper chloride, and isopropyl alcohol can be used.
Copper chloride or the like is used for each of these. Generally, polyvalent alcohol which also has the effect of improving the crosslink density of the resin is preferable, and ethylene glycol is particularly preferable. As the soluble salt, particularly high solubility, potassium carbonate, barium chloride, potassium iodide, lithium chloride,
Sodium bromide and calcium chloride are preferred. In order to obtain the effects of making bubbles finer and increasing the crosslink density as a bubble nucleating agent, it is necessary to add the polyhydric alcohol to a certain extent or more. The amount is preferably 0.5 part of salt with respect to 100 parts by weight of polyol. With this configuration, it is possible to obtain a foam having high resin strength and fine bubbles.

When the foaming agent of the present invention is used, the following carbonate compound, ester or epoxide may be added to the resin raw material for the purpose of reducing the viscosity of the raw material and improving the compatibility of the foaming agent with the raw material. preferable. It is preferable that these additives do not easily vaporize, and compounds having a boiling point of 100 ° C. or higher are preferable. In addition, 30 of resin raw materials
It is preferable to add it in a proportion of not more than wt% in order to reduce the thermal conductivity of the resin. The organic carbonate compound used here is preferably dimethyl carbonate, propylene carbonate, 1,2-butylene carbonate, hexylene carbonate, styrene carbonate, vinyl ethylene carbonate, phenyl ethylene carbonate, or the like, which is produced by an addition reaction of epoxide and carbon dioxide. Carbonate compounds are also preferred. As the ester, phthalic acid ester, phosphoric acid ester, adipic acid ester, azelaic acid ester, sebacic acid ester, acrylic acid ester, methacrylic acid ester and the like are used. Typical epoxides are epoxy butyl stearate, epoxy octyl stearate, glycidyl benzoate and the like. An epoxide that fixes carbon dioxide as described below is also preferable.

Further, as an oxygen absorbent for suppressing the oxidation and decomposition of the blowing agent of the present invention, Cu, Cu ₂ O, Fe
Magnetite, cobalt, nickel, zinc, Na ₂ S ₂ O
A foam in which ₃ or the like is mixed is preferable because it retains a high heat insulating property for a long time. In addition, Cu, Na ₂ S ₂ O
₃ etc. also has the effect of reducing free iodine and keeping the foam stable.

When a fluorinated iodohydrocarbon is used as a foaming agent, a non-amine type polyol is preferably used as the polyol in order to improve the foamability. In general, a polyol, which is a urethane raw material used for a heat insulating material, is used as a composition to which an amine as a polymerization reaction initiator, ethanolamine as a reaction preparation agent and the like are added. However, these amine-based polyols
It should be avoided as it interacts with fluorinated iodohydrocarbons. Therefore, it is preferable to improve the heat insulating property by using a non-amine type polyol. Examples of such polyols include polyhydric alcohols, polyether polyols obtained by adding alkylene oxides using saccharides as reaction initiators, polyhydric alcohol-polycarboxylic acid condensation systems, or polyesters of cyclic ester ring-opening polymer systems. Polyols are preferable, and compounds having two or more phenolic hydroxyl groups can also be used. Further, a composition in which polyhydric alcohol is directly mixed may be used. The method for producing a resin foam as a composition in which a fluorinated iodohydrocarbon is mixed with polyisocyanate is characterized in that the fluorinated iodohydrocarbon can be stably dispersed in the polyisocyanate. It is a method of emulsifying the foaming agent in polyisocyanate instead of polyol in the production. In addition, this method is preferable because bubbles can be made finer.

The fluorinated iodohydrocarbon and a base such as a non-conjugated amine or ammonium salt, or a quaternary ammonium salt easily form a complex compound. The complex compound has a different complex formation state depending on the combination of compounds.
For example, heptafluoro-2-iodopropane and N,
The interaction with N, N ′, N′-tetramethylhexamethylenediamine is very strong, and a dark brown solid is produced when iodine and amine are mixed at a molar ratio of 1: 1. When this was isolated and dissolved in water, it was separated into two layers, and it was confirmed that the upper layer was composed of water and the tetramethylhexamethylenediamine, and the lower layer was composed of a small amount of tetramethylhexamethylenediamine and the heptafluoro-2-iodopropane. Was done. From this, it is considered that the complex compound is formed. This complex compound did not decompose with light.

When an imidazole compound, which is a kind of aromatic amine, was mixed with heptafluoro-2-iodopropane in the same manner, no complex compound solid was formed at any mixing ratio. However, when the mixture was heated, heptafluoro-2-iodopropane, which should normally boil at 40 ° C., did not boil when heated to 70 ° C. or higher, and finally boiled at 80 ° C. or higher. When water was added to this, it separated into two layers and boiled around the boiling point of heptafluoro-2-iodopropane. The upper layer of this separation layer was again a mixture of water and amine, and the lower layer was mainly composed of iodopropane. From this, it is considered that a complex compound is formed by weak interaction. In addition, heptafluoro-1-iodopropane, which is an isomer of heptafluoro-2-iodopropane, was converted into N, N,
When mixed with N ′, N′-tetramethylhexamethylenediamine, a solid complex compound was not obtained, and a liquid did not boil even at 80 ° C. or higher. When water is added, it separates into two layers, so it is considered that a complex compound is formed although it is weak.

As described above, the complex compound of a fluorinated iodohydrocarbon and an amine is in a liquid state or a solid state depending on the compound to be used, and the bonding force is different. It is possible to form a heat insulating resin foam having the above. As a general tendency, the lower the amine compound used, the stronger the bond strength, and the more fluorinated iodohydrocarbon used, the stronger the iodine bond, the stronger the bond strength.

Complex compounds suitable for use in the present invention are:
It is easily decomposed by heat of resin reaction, and the fluorinated iodohydrocarbon produced by the decomposition functions as a foaming agent. Such preferred complex compounds are selected from complex compounds of fluorinated iodohydrocarbons with one of non-conjugated tertiary amines, ammonium salts and quaternary ammonium salts. When this complex compound is used together with a urethane reaction catalyst, the complex compound also functions as a temperature-sensitive urethane reaction catalyst. Usually, tertiary amines are used as urethane reaction catalysts. Such a complex compound of a tertiary amine and a fluorinated iodohydrocarbon is most preferred for the present invention. This complex compound itself has a very low catalytic activity for the urethane reaction, but when the resin reaction heat is generated and the complex compound is separated into amine and fluorinated iodohydrocarbon,
The separated amine acts as a urethane reaction catalyst. At this time, it is preferable that the fluorinated iodohydrocarbon is present in the foamed resin composition by vaporizing to become a foaming agent or forming a complex compound with the amine again after the resin reaction is completed. Conventionally, when amine, which is a urethane reaction catalyst, remains in the resin, it causes deterioration of the resin and deterioration of heat insulating performance.
However, as described above, when the fluorinated iodohydrocarbon forms a complex compound with the amine again after the completion of the resin reaction, such inconvenience can be eliminated. Also, first grade,
Secondary amines are not commonly used as urethane reaction catalysts, but complex compounds with fluorinated iodohydrocarbons
It is preferable because it serves as a weak catalyst for the urethane reaction and further reacts with isocyanate to form a resin.

Further, since this complex compound is decomposed by addition of water, control using water is possible. And
When the complex compound serves as a temperature-sensitive urethane reaction catalyst, it is possible to control the foaming reaction by utilizing the fact that when the complex compound is decomposed by adding water, the activity for the urethane reaction is increased. Since water also acts as a foaming agent, it is most preferable to add 10 parts by weight or less to 100 parts by weight of the polyol.

Examples of the substance used as the primary amine include alkylamines such as ethylamine, butylamine, propylamine and hexylamine, amino alcohols such as ethanolamine, aromatic rings represented by aminobenzene, aminobenzimidazole and the like. A compound to which a primary amine is added, an amino group-containing organic acid such as anthranilic acid, and the like are preferable. The secondary amine is preferably an alkyl group addition compound of the above primary amine, a cyclic amine, sulfamic acid, an amino acid or the like. As the tertiary amine, an alkyl group adduct of the secondary amine and the like are suitable.
In particular, a general tertiary amine compound is also suitable as a compound having urethane reaction catalytic activity. Commonly used amine-based urethane reaction catalysts include N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′,
N ', N'-pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, N, N', N "-tris (3-dimethylaminopropyl) hexahydro-s-triazine, N-trioxyethylene-N, N-dimethylamine, tri Ethylenediamine, N, N-dimethylhexylamine, N, N-dimethylbenzylamine, N-
Methylmorpholine and the like are preferable.

Ammonium salts and quaternary ammonium salts are generally organic acid salts of amines, phenol salts,
Halogen salts are desirable, tetrabutylammonium bromide, tetrabutylammonium iodide, 1,
Phenol salts of 8-diazabicyclo- (5,4,0) undecene-7 and the like are preferable because they can be used not only as a urethane reaction catalyst, but also as a carbon dioxide-immobilized catalyst in which an epoxide reacts with carbon dioxide to immobilize it. . The urethane reaction catalyst that can be added to the complex compound is preferably an organic tin compound, a metal salt of an organic acid, an aromatic amine, or an organic phosphorus compound. This is because these compounds do not easily interact with halogens such as fluorinated iodohydrocarbons and do not lower the urethane reaction catalyst activity.

As the organic tin compound, dibutyltin dilaurate, dibutyltin diacetate, dioctyltin diversate, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin oxide, dioctyltin dialkylmercaptan and the like are preferable. As the metal salt of an organic acid, zinc stearate, potassium acetate, potassium octylate, an alkali metal salt of formic acid and the like are preferable. These catalysts are preferable because they are effective in forming an isocyanurate structure in the resin and impart flame retardancy. Aromatic amines are preferable because they are amines but have a very weak interaction with fluorinated iodohydrocarbons and do not lower the urethane reaction catalyst activity. Common aromatic amines act as weak catalysts. In particular, compounds having pyrrole, imidazole, pyrimidine, triazine, benzimidazole as a skeleton and the like are preferable. The organic phosphorus compound is preferably a compound having a phospholene oxide skeleton and is suitable for increasing the strength of the resin foam by a carbodiimide bond. Further, tetraphenylphosphonate, triphenylmethylphosphonate, tetrabutylphosphonate and the like are preferable because they act not only as a urethane reaction catalyst but also as a carbon dioxide fixing catalyst.

In the present invention, preferable compounds used for forming a carbonate compound in a resin foam by reacting carbon dioxide with an epoxide to immobilize it are shown below. Examples of the epoxide added to the resin raw material composition to fix carbon dioxide include propylene oxide and butylene oxide, which have a low boiling point and also act as a foaming agent. Further, compounds having an epoxy ring in the alkyl chain such as octylene oxide and hexylene oxide; glycidyl ether compounds such as methyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and methacrylic acid glycidyl ether;
Epichlorohydrin, glycidol, styrene oxide, N- (2,3-epoxypropyl) phthalimide,
3-Glycidyloxypropyltrimethylsilane and the like are monofunctional liquid or solid epoxides at room temperature, and are preferable because they not only fix carbon dioxide but also act as the aforementioned additives in the resin composition.

The polyfunctional epoxides include hydroquinone diglycidyl ether, resorcin diglycidyl ether, neopentyl glycidyl ether, pentaerythritol polyglycidyl ether, orthophthalic acid diglycidyl ether, sorbitol tetraglycidyl ether, hexamethylene diol diglycidyl ether, etc. Besides, there are polyglycerol triglycidyl ether and the like. Since these polyfunctional epoxides can be polymerized into a resin material, they are preferable not only for fixing carbon dioxide but also as a raw material for a foamed resin composition.

As the nucleophilic agent as the carbon dioxide fixing catalyst, halogen ions such as chlorine, bromine and iodine are preferable, and onium salts are preferable. Among the onium salts, effective ones are ammonium salts represented by tetrabutylammonium bromide and tetrabutylammonium iodide. Further, phosphonium salts represented by tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, and sulfonium salts represented by tributylsulfonium bromide are also preferable. Further, a complex compound of an amine compound and a halide is also used. A complex compound of a fluorinated iodohydrocarbon as a blowing agent and an amine or ammonium salt or a quaternary ammonium salt is also used. Further, a complex compound of a tertiary amine, an ammonium salt or a quaternary ammonium salt and a fluorinated iodohydrocarbon is preferable because it easily produces a halogen ion.

Zinc compounds and tin compounds are used as electrophiles as carbon dioxide fixing catalysts. Zinc compounds include zinc chloride, zinc bromide, zinc iodide, zinc acetate,
Examples include zinc stearate, zinc acetylacetonate, and zinc citrate. As the tin compound, tin halides such as tin chloride; organotin compounds such as dibutyltin dilaurate, dioctyltin diversate and dibutyltin diacetate are preferable. These are useful in the present invention because they are substances that are also used as urethane reaction catalysts. Also, an alkali halide can be used as a carbon dioxide-immobilized catalyst. Lithium bromide,
Halides of lithium iodide, lithium chloride; sodium and potassium are preferred. Further, iron chloride, copper chloride, cobalt chloride, manganese chloride, chromium chloride and the like are also preferable carbon dioxide fixed catalysts.

The present invention provides a composition in which a carbon dioxide-immobilized catalyst comprising the nucleophile and / or the electrophile is mixed with isocyanate together with fluorinated iodohydrocarbon. Also, the epoxide is mixed with the polyol. It is preferable to mix these isocyanate composition and polyol composition to carry out the foaming reaction. As a result, the carbon dioxide immobilization reaction can be activated and the efficiency can be increased. That is, in order for the epoxide to sufficiently immobilize carbon dioxide, it is useful to store the carbon dioxide-immobilized catalyst stably until it comes into contact with carbon dioxide. The carbon dioxide-immobilized catalyst can be stably stored by adding the carbon dioxide-immobilized catalyst to the isocyanate and further mixing the fluorinated iodohydrocarbon. Further, since the carbon dioxide-immobilized catalyst interacts with the fluorinated iodohydrocarbon and is stabilized, there is no carbon dioxide-immobilized catalyst effect in this state. When the isocyanate composition and the polyol composition are mixed and the fluorinated iodohydrocarbon is vaporized by the heat of the resin reaction, a carbon dioxide-immobilizing catalytic action occurs.

Further, it is preferable to previously add the fluorinated iodohydrocarbon and the carbon dioxide-immobilized catalyst as a complex compound because the epoxide and the carbon dioxide react more efficiently. Further, it is also preferable that the fluorinated iodinated hydrocarbon forms a complex compound with an amine to generate a free iodo ion to serve as a carbon dioxide-immobilized catalyst. Also in this case, it is preferable to separate the epoxide and the carbon dioxide-immobilized catalyst from each other. Since it is stabilized by complex formation, unnecessary reaction does not occur and the epoxide reacts efficiently with carbon dioxide. Further, it is also preferable that the carbon dioxide-immobilized catalyst, which was active by the heat of reaction after the carbon dioxide is immobilized, slowly returns to the complex compound with the fluorinated iodohydrocarbon and loses the activity because it does not cause resin deterioration.

The role of the foam stabilizer used in the present invention is to increase the compatibility of the raw materials and to serve as cell nuclei to reduce the surface tension of the resin raw material and stabilize the bubbles during foaming. In particular, a silicon-based surfactant is used.
In the present invention, since the foaming agent is a compound having fluorine, in order to stabilize the bubbles, a dimethylsiloxane-oxyalkylene copolymer and a dimethylsiloxane-oxyalkylene copolymer having a fluoroalkyl group in the molecule are used. It is preferable to use a foam stabilizer containing the same. With conventional silicone-based surfactants, when using a fluorine-based foaming agent,
Bubbles are difficult to stabilize, resulting in non-uniformity and foam breaking during the foaming process. The foam stabilizer having a fluorinated alkyl group is easy to mix with the foaming agent of the present invention and has a conventional bubble stabilizing effect. The silicone-based surfactant used as the foam stabilizer in the present invention includes:
There is something shown in.

[0062]

[Chemical 4]

[0063] (wherein, R, R ', R "are each independently _{-H, -COCH 3, - (CH 2} ) x CH 3 or - (CF _{2) y}
CF ₃ and Me is a methyl group. Further, a and b are 1 to 10 and x and y are 1 to 18) The polyol used in the present invention is a conventionally used polyether except for the purpose of using a fluorinated iodohydrocarbon as a foaming agent. Suitable are polyols and polyester polyols. In addition, a polyol having a large number of hydroxyl groups synthesized from a polyhydric alcohol in its molecule is suitable for obtaining hardness or controlling reactivity. In the polyol molecule, a tertiary amine together with a hydroxyl group,
Catalyst-containing polyols containing phosphorus or halogen, flame-retardant polyols, aromatic polyols are also suitable. Adding water to the polyol to improve foamability is a preferred technique. When water is added together with the blowing agent having a relatively high boiling point in the present invention, a low-density foam can be formed, and bubbles can be made uniform and fine. Similarly, by adding alcohol, due to the heat of reaction when the alcohol reacts with the isocyanate,
Like water, the foamability of the foaming agent can be improved, which is preferable. Suitable alcohols that can be used include methanol, ethanol, ethylene glycol, glycerin, pentaerythritol, α-methyl-D-glucoside, trimethylolpropane, sorbitol and sucrose.

As the isocyanate used in the present invention, diphenylmethane diisocyanate type, tolylene diisocyanate type, xylylene diisocyanate, metaxylylene diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate and the like are suitable. ing. As the urethane reaction catalyst used in the present invention, it is necessary to select a most effective catalyst such as a gelling catalyst, a foaming catalyst, and a delay catalyst depending on the reactivity of the urethane raw material. Commonly used catalysts are tertiary amines and organometallic compounds, and amine-based catalysts include monoamines, diamines, triamines, cyclic amines, alcohol amines and ether amines. Of the organometallic compounds, organotin compounds are most often used. In the present invention, since the boiling point of the blowing agent is from room temperature to 70 ° C., a general formulation catalyst is used. However, when the azeotropic point is extremely low or high, it is necessary to use properly or mix various catalysts. Further, water also reacts with isocyanate to form a urea bond, which greatly contributes to the physical properties of urethane, and therefore may be added to improve the crosslink density.

The flame retardants used in the present invention include phosphates, bromine-phosphorus compounds, organic bromine compounds and the like. In particular, phosphorus-based flame retardants such as tris (β-chloroethyl) phosphate, tricresyl phosphate, and trixylenyl phosphate are suitable for the present invention because they produce little toxic gas during combustion. Further, by adding additives such as a hydrolysis inhibitor and an antioxidant, a long-term physical property stabilizing effect can be obtained. The foaming agent of the present invention has a boiling point of 40 to 7
Since it is about 0 ° C., it is easy to obtain a foamed foam having a proper performance by mixing it with a conventional polyol composition as a sole foaming agent, and to heat the foamed foam by 10 to 40% as compared with the conventional cyclopentane foamed foam. A foam with low conductivity is obtained.

Hereinafter, the present invention will be specifically described with reference to the embodiments. [Example 1] As shown in Table 1, polyurethane foams were prepared by using raw materials of various formulations, and their thermal conductivity and other physical properties were measured. Here, the polyol A in the raw material is an amine-based polyether polyol composition having a hydroxyl value of 449 mg.
KOH / g, Polyol B is a sorbitol-based polyether polyol with a hydroxyl value of 420 mg KOH / g
belongs to. Further, the foam stabilizer A is a silicon-based surfactant (trade name TY19 of Takeda Pharmaceutical Co., Ltd.), and the foam stabilizer B is a fluorinated silicon-based surfactant (trade name X-70- of Shin-Etsu Chemical).
090). The catalyst A is a catalyst mainly containing N, N, N ′, N′-tetramethylhexamethylenediamine (Kao's Kaolizer No. 1), and the catalyst B is an imidazole-based composite catalyst (Kao's Kaolizer No. 300). . The foaming agent A is heptafluoro-2-iodopropane, the foaming agent B is a mixture of heptafluoro-2-iodopropane and cyclopentane in a molar ratio of 1: 2, and the foaming agent C.
Is cyclopentane. The isocyanate, which is shown as MDI in Table 1, is a composition containing 31.4 wt% of isocyanate groups per gram (Takeda's trade name Luplanate M-20S). Additive A is propylene carbonate.

The foam was prepared as follows. First,
Sample No. Except for 1-5, a foam stabilizer, a catalyst,
A premix was prepared by mixing water and a foaming agent. Then, the prepared polyol premix component and isocyanate component are mixed at a predetermined mixing ratio, mixed and stirred by a high-pressure foaming machine, and filled in a space portion constituted by an outer box 1 and an inner box 3 as shown in FIG. And foamed to obtain polyurethane foam 2. Sample No. For 1-5, the foaming agent and foam stabilizer were mixed with the isocyanate.

As a comparative example, an example of foam using cyclopentane as a foaming agent (Sample No. 1-6) is shown in the table. The purpose of formulation of each sample is shown below. Sample No.
No. 1-1 is an example in which a foaming agent fluorinated iodohydrocarbon and water foaming are used in combination. Sample No. Nos. 1 and 2 are formulations for the purpose of improving foamability by using a sorbitol-based polyether polyol which is a non-amine-based polyol and further adding a carbonate compound. Sample No. Nos. 1 to 3 are formulations using a mixture of fluorinated iodohydrocarbon and cyclopentane as a foaming agent and aiming at flame retardancy. Sample N
o. Nos. 1 to 4 had the same composition as that of the comparative example using cyclopentane as the foaming agent except that fluorinated iodohydrocarbon was used as the foaming agent. Sample No. 1-5 is a formulation using a non-amine-based polyol and a foam stabilizer. Sample No. of the comparative example. Nos. 1 to 6 are optimum blends with no water added. On the other hand, the sample N of the embodiment of the present invention
o. In Nos. 1-1 to 1-3 and 1-5, the amount of isocyanate was adjusted to be the same as that of Sample No. 1 in consideration of the reaction between isocyanate and water due to the addition of water. The catalyst B is used in an amount larger than 1-6 and considering the addition of water.

In each of the following Tables 1 to 5, the blending amount of the raw material of each sample is expressed in parts by weight. The unit of physical properties of the foam is as follows. Unit of foam density: kg / m ³ Thermal conductivity: Ratio when cyclopentane foam (Sample No. 1-6) is set to 1 Unit of cell diameter: μm Unit of compressive strength: kg weight / cm ²

[0070]

[Table 1]

As shown in Table 1, heptafluoro-
The foam using 2-iodopropane as the foaming agent (Sample No. 1-4) has about 10% of the same raw material formulation as the conventional foam using cyclopentane as the foaming agent.
It showed a low thermal conductivity of about%. However, the foam density was high and the cell diameter was also large. On the other hand, the sample No. of the prescription with water added. The sample No. 1-1 had a low thermal conductivity, and the physical properties such as density and bubble shape were improved. In order to form a foam having a lower thermal conductivity, when a sorbitol-based polyether polyol was used in 70% of the polyol (Sample No. 1-2), the foam exhibited a lower thermal conductivity. This is sample No. This is because the foamability was improved and the foam density was reduced as compared with 1-1. In addition, the bubble diameter was uniform and miniaturized. This is likely due to the propylene carbonate used as an additive. Thus, the thermal conductivity of the foam is about 30% as compared with the foam of the comparative example using cyclopentane as the blowing agent.
I was able to lower it. The improvement of the polyol and additives have significantly improved the heat insulation performance.

Next, in the case of Sample No. 1 in which a mixture with cyclopentane was used as a foaming agent. Foams 1-3 are almost sample N
o. The performance was similar to that of 1-2, and the thermal conductivity was lower than that of the comparative example using cyclopentane alone as the foaming agent. To evaluate the flammability of the foam, use the foam 1 × 1 ×
When the sample cut to 5 cm was ignited, the sample No. Sample Nos. 1-6 burned completely, but sample No. In 1-3, the fire was extinguished immediately after it ignited. Heptafluoro-2
-Sample No. using iodopropane as a foaming agent. In Nos. 1 and 2, fluorinated iodohydrocarbons were also mixed with flammable cyclopentane for extinguishing fire, and it was found that they exhibited flame retardancy and self-extinguishing functions. Further, the foam stabilizer was changed to form a foam in order to modify the compatibility of the foaming agent with other compositions. In the formulation in which only the fluorine-based surfactant was added, the bubbles were crushed during foaming, and the bubbles became large, resulting in high thermal conductivity. However, sample No. 1 was used except that this fluorine-based surfactant and a conventionally used silicon-based surfactant were mixed at a weight ratio of 1: 2. When the same formulation as 1-1 was used, the compatibility of the premix was improved, the foamability was enhanced, and the cells were stabilized at the same time, so that a foam having fine cells of 270 microns could be obtained. The thermal conductivity of this foam was 0.73.

Sample No. In Nos. 1-5, the mixture foam stabilizer was used, and an isocyanate premix was prepared by mixing the foam stabilizer with an isocyanate. This isocyanate premix was mixed with the polyol composition and foamed. According to this formulation, the thermal conductivity of the resulting foam is about 40% compared to the comparative example using cyclopentane as the blowing agent.
It was possible to obtain a urethane foam having a low property and exhibiting the optimum physical properties as a heat insulating material. In addition, this foam stabilizer and additive A
When added in combination, the thermal conductivity of 0.6
Foam strength is 0.95 kg / m
^{At 3} , the strength became slightly lower. Next, sample No. When 5 parts of magnetite powder was dispersed in the isocyanate premix having the formulation of 1-5, the thermal conductivity of the obtained foam was 0.66 of the comparative example, and almost no foam thermal conductivity was obtained by adding magnetite. It didn't change. In addition, the foam thermal conductivity after the lapse of 3 months was 0.67, and almost no deterioration of the heat insulating property was recognized. On the other hand, when magnetite, which is an oxygen absorber, was not added, the thermal conductivity was 0.75, which was a considerable decrease in thermal insulation after 3 months.
Therefore, it was found that the addition of the oxygen absorbent shows good heat insulating performance even in the long term.

Example 2 A foam was prepared according to Example 1 and its characteristics were evaluated. Table 2 shows the raw material formulation and the properties of the resulting foam. The foaming agent D is hexafluoropropene dimer, the foaming agent E is a mixture of heptafluoro-2-iodopropane and hexafluoropropene dimer in a molar ratio of 1: 1, and the foaming agent F is heptafluoro-2-iodopropane and hexafluoropropene dimer. And cyclopentane in a molar ratio of 1: 1: 2. For other materials, the same substances as in Table 1 are shown.

The purpose of prescribing each sample is shown below. Sample N
o. No. 2-1 is a formulation in which a blowing agent perfluoroalkene and water foaming are used in combination. Sample No. No. 2-2 is a formulation using a mixture of perfluoroalkene and fluorinated iodohydrocarbon as a foaming agent. Sample No. 2-3 is a ternary foaming agent formulation of perfluoroalkene, fluorinated iodohydrocarbon and cyclopentane. Sample No. Nos. 2-4 have the same formulation as the comparative example except that perfluoroalkene was used as the blowing agent. Sample No. No. 2-5 is a formulation intended for the combined effect of the mixture foam stabilizer and water foaming. Sample No. 1-6
Is a comparative example used in Example 1.

[0076]

[Table 2]

Sample No. using hexafluoropropene dimer as a foaming agent The foam according to No. 2-4 was an unstable composition in which the premix was in an emulsion state and separated in 3 to 4 hours, so that the foam density was high and the bubbles were non-uniform. Sample No. In No. 2-1, the amount of water added is 3 parts and the amount of heptafluoropropene dimer is reduced. According to this formulation, the foamability could be improved to some extent. However, the gas contains nearly 50% carbon dioxide gas. For this reason, the thermal conductivity was high and was slightly lower than that of the comparative example. On the other hand, sample No. Two
The foam of No. 3 had a thermal conductivity of about 37% lower than that of the comparative example (using cyclopentane as the foaming agent).
This is because heptafluoro-2-iodopropane and cyclopentane have a function of considerably lowering the viscosity of the emulsion of the premix, and the emulsion is a cell nucleus, so that the bubbles are uniform and fine. . In addition, the sample No. It is considered that the 2-3 foaming agents exhibit a behavior close to that of azeotrope and have a considerably low boiling point, and exhibit a good foaming property similar to that when foaming using a low boiling point compound. In addition, when the flammability of the foam was evaluated, it was found that sample No. Sample N using cyclopentane showing the same flammability as the mixed blowing agent of 2-1, 2,4 heptafluoropropene dimer and carbon dioxide
o. It was far more flame retardant than 1-6.

When a fluorinated silicone surfactant (foam stabilizer B) is used in place of the foam stabilizer, a phenomenon occurs in which the foam collapses during the reaction growth of the foam, and the foam can be formed. There wasn't. However, the sample No. In 2-5, when a foam stabilizer prepared by mixing a fluorinated silicone surfactant and a silicon-based surfactant (foam stabilizer A) was used, the stability of the premix emulsion was improved and the phase was maintained for 1 week or longer. The emulsion morphology was retained without separation. Further, the obtained foam had fine cells, and the thermal conductivity thereof was about 30% lower than that of the comparative example. Sample N
o. In 2-5, the foaming agent is hexafluoropropene dimer alone, but the amount of water can be reduced to obtain the foam by using the mixed foam stabilizer at the same time. In that case, since the carbon dioxide gas decreased, the thermal conductivity could be further reduced by about 5%. Sample No.
When propylene carbonate was added to the formulation No. 2-4, the resulting foam had a density of about 41 kg / m ³ and a thermal conductivity of about 15% lower, which was effective as an additive. Similarly, when isomers of heptafluoropropene dimer were isolated and foams were made by using each as a foaming agent and evaluated, foams having almost the same heat insulation performance were obtained.

[Example 3] An example in which a hydrogen-containing fluorinated morpholine derivative is used as a foaming agent is shown. The production of the foam is the same as in Example 1. Table 3 summarizes the formulation of each sample and the properties of the resulting foam. The blowing agent G is 3H-octafluoromorpholine, the blowing agent H is 3H-heptafluoro-4-trifluoromethylmorpholine, and the blowing agent I is 3H-heptafluoro-4-trifluoromethylmorpholine and cyclopentane. It is a mixture with a molar ratio of 1: 1 and the blowing agent J is 3H-heptafluoro-4-.
It is a mixture of trifluoromethylmorpholine and isopentane in a molar ratio of 1: 1. Additive B is neopentyl diglycidyl ether. The foam stabilizer C is the foam stabilizers A and B.
Is a mixture with a weight ratio of 3: 1. Other materials are listed in Table 1.
Indicates the same substance as.

The purpose of each prescription in the table will be described. Sample No. 3-1 and No. 3-2 is a formulation in which a foaming agent hydrogen-containing fluorinated morpholine derivative and water foaming are used in combination.
Each of the different hydrogen-containing fluorinated morpholine derivatives is used. Sample No. No. 3-3 is a formulation using a mixture of a hydrogen-containing fluorinated morpholine derivative and cyclopentane as a foaming agent. Sample No. No. 3-4 is a formulation using a mixture of hydrogen-containing fluorinated morpholine derivative and isopentane as a foaming agent. Sample No. No. 3-5 is a formulation in which an epoxide is mixed as an additive and foaming is performed without using water. Sample No. Nos. 1 to 6 are comparative examples used in Example 1.

[0081]

[Table 3]

Sample No. 3 in which the foaming agent was 3H-octafluoromorpholine alone and water foaming was also used. Sample No. 3 using foam according to 3-1 and 3H-heptafluoro-4-trifluoromethylmorpholine in place of 3H-octafluoromorpholine. The foam according to the formulation of 3-2 had lower thermal conductivity than that in the case where water was not added. However, the foam density was relatively high and the cell diameter was also large. The compatibility between the polyol and the foaming agent was relatively good, and a premix emulsion having a low viscosity similar to that of the comparative example (Sample No. 1-6) was obtained. The thermal conductivity of the foam was 10% or more lower than that of the comparative example, but the foam density was high. Therefore, it is necessary to modify the foam to further improve the performance.

Since the foaming agent H has a slightly high boiling point, it has a poor foaming property and the density of the obtained foam is high. Therefore,
Sample No. 1 in which cyclopentane and isopentane having low boiling points were mixed in the foaming agent H, respectively. 3-3 and No. When foamed according to the formulation of No. 3-4, the density of the obtained foam was lowered due to the improvement of the foamability, and the thermal conductivity was also reduced accordingly. Sample No. In 3-3, a foam having low thermal conductivity was obtained, and the value could be reduced by nearly 30% as compared with the comparative example. However, since the thermal conductivity of the blowing agent cyclopentane to be mixed is higher than that of the morpholine derivative, the thermal conductivity of the foam is increased by being dragged by the blowing agent cyclopentane having a high thermal conductivity. Therefore, the sample No. 3-3
In the above formulation, when heptafluoro-1-iodopropane was used instead of cyclopentane, the thermal conductivity of the obtained foam was very low due to the mixing effect, and was 30% or more lower than that of the comparative example.

Next, by adding an epoxide and using only a morpholine derivative as a foaming agent, a foam having a lower thermal conductivity was prepared.
o. A foam was obtained in 3-5. As a foaming agent, 3H-octafluoromorpholine was used, and 5 parts of neopentyl diglycidyl ether was added as an additive to prepare a premix. When this premix was mixed with an isocyanate, the foaming time was shorter than that in the case where no epoxide was added, and the foamability was better than in other formulations. The obtained foam had a low density and the cell diameter was made fine and uniform by the addition of the foam stabilizer, so that it was a urethane foam having very good performance.

Example 4 Next, in addition to the addition of each foaming agent, an example for confirming the effect of the additive will be shown. The formulation of each sample and the properties of the resulting foam are shown in Table 4. The foaming agent K is a complex compound (liquid state) of heptafluoro-2-iodopropane and tetrabutylammonium bromide. Additive C is potassium carbonate, C ′ is ethylene glycol, and additive C is simultaneously used as a liquid dissolved in C ′. Further, the additive D is sodium thiosulfate, and the additive D ′ is
It is water that dissolves it.

The formulation of each sample in the table will be described. Sample No. 4-1 is a formulation using a mixture of a fluorinated iodohydrocarbon and a perfluoroalkene as a foaming agent. Sample No. No. 4-2 is a formulation in which potassium carbonate dissolved in ethylene glycol is added to make bubbles fine. Sample No. No. 4-3 is a formulation in which sodium thiosulfate as a reducing agent is added in an aqueous solution. The sodium thiosulfate aqueous solution was mixed with isocyanate at the raw material preparation stage. Sample N
o. 4-4 is a prescription for the purpose of using a complex compound of a fluorinated iodohydrocarbon and an amine compound and using it as a part of a foaming agent. The amount of perfluoroalkene added as a foaming agent liquid. Is 1 mol per 1 mol of the fluorinated iodohydrocarbon forming a complex compound. In addition, it is an example in which water is added as a reaction control agent. Sample N
o. Nos. 4 and 5 are formulations in which water was added to the mixed foaming agent for comparison. Sample No. Nos. 1 to 6 are comparative examples used in Example 1.

[0087]

[Table 4]

Also in the sample in which each foaming agent was mixed, a heat insulating foam having a conductivity lower than that of the comparative example by 20% or more was obtained. In addition, sample No. The foam according to Sample Nos. 4-5 has a small bubble diameter, and thus the sample No. Four
Compared with -1, the density was lower and the thermal conductivity was lower. It was confirmed that, similarly to Examples 1, 2 and 3, by adding different foaming agents, physical properties such as strength as well as thermal conductivity of the foam can be improved. In addition, the sample No. In the foam of No. 4-2, the salt dissolved in ethylene glycol as an additive is considered to be a cell nucleus, and the cell diameter was very small. Furthermore, when an aqueous solution of sodium thiosulfate is added to isocyanate, the foam diameter of the obtained foam is further refined.

Sample No. In No. 4-4, a complex compound of an amine compound and a fluorinated iodohydrocarbon was added to consider heptafluoro-2-iodopropane in the complex compound as a foaming agent, and the total amount of the foaming agent was Sample No. The same amount as 4-1 was added, and a small amount of water was added. A low thermal conductivity rigid urethane foam with good foam density was formed. When the foam was left in a place exposed to sunlight and the change in thermal conductivity with time was examined, in the comparative example, the thermal conductivity hardly changed even after one month. In the urethane obtained by using the foaming agent mixed with heptafluoro-2-iodopropane, Sample No. The thermal conductivity increased considerably in 4-1, 2, and 5. This is heptafluoro-2
-It seems that the decomposition of iodopropane is involved. On the other hand, sample No. In 4-3, the thermal conductivity did not change. It is considered that the added sodium thiosulfate suppresses the decomposition of heptafluoro-2-iodopropane. Also, when measuring the foam strength after one month,
Sample No. Except for 4-3, a considerable decrease in strength was observed.

Sample No. In 4-4, a complex compound of heptafluoro-2-iodopropane and tetrabutylammonium bromide was added. Heptafluoro-2-
For the total amount of iodopropane, the sample No. According to 4-1, the molar ratio to hexafluoropropene dimer is 1: 1
And As a result, it was possible to obtain a foam in which the foaming property could be improved by using the same polyol raw material as the conventional one and the cells had relatively fine bubbles.

Example 5 An example in which an epoxide is added will be shown. The formulation of each sample and the properties of the resulting foam are shown in Table 5. The foaming agent L is a complex compound of heptafluoro-2-iodopropane and tetramethylhexamethylenediamine, and the total amount of the foaming agent in the complex compound and the foaming agent added alone is equal to that of the sample No. 5-2 and 5-3
Is the same as Catalyst C is dibutyltin dilaurate. Additive E is phenyl glycidyl ether, Additive F
Is a carbon dioxide-immobilized catalyst tetrabutylammonium bromide. Others are the same as the above-mentioned embodiment.

The formulation of each sample is described below. Sample N
o. No. 5-1 is a normal formulation using fluorinated iodohydrocarbon as a foaming agent. Sample No. 5-2 is the addition of epoxide to the fluorinated iodohydrocarbon blowing agent,
It is a formulation for the purpose of absorbing and fixing carbon dioxide generated by the reaction between water and isocyanate. Sample No. 5-3 is sample No. An example in which a polyol prepared by mixing an epoxide in which a carbon dioxide-immobilized catalyst is dissolved and a foaming agent (fluorinated iodohydrocarbon) is prepared according to 5-2, and is mixed with an isocyanate to foam. Is. Sample No. No. 5-4 is a formulation in which a complex compound produced by mixing fluorinated iodohydrocarbon with a carbon dioxide-immobilized catalyst is added to isocyanate to expect high yield of carbon dioxide immobilization. Sample No. No. 5-5 is a formulation in which cyclopentane is used as a foaming agent and epoxide is added to fix carbon dioxide. Sample No. 1
-6 is a comparative example used in Example 1.

[0093]

[Table 5]

Sample No. 5-5 is water 1 in the formulation of the comparative example
By adding the additives E and F, carbon dioxide in the foamed resin was absorbed and the thermal conductivity could be reduced by 10% or more. This thermal conductivity further decreased by about 20% after 7 days. When the carbon dioxide in the foam was analyzed by gas chromatography, the amount of carbon dioxide initially generated was almost gone. A mixture of heptafluoro-2-iodopropane and water was used as a foaming agent, and the additives E and F were added thereto. The foam according to Sample No. 5-2 has a low thermal conductivity of the foaming agent. Similar to 5-1, it has a lower foam thermal conductivity than the comparative example. Further, the sample No. 5-2
Then, as a result of the absorption of carbon dioxide, the thermal conductivity decreased by 33% from the comparative example one week later. Sample No. 5-3
But it was almost the same. Sample No. When the 5-2 and 5-3 foams were analyzed by infrared absorption spectrum, almost 100% of the epoxide was a carbonate compound reacted with carbon dioxide, and it is considered that carbon dioxide was immobilized at a high yield. To be

Sample No. No. 5-4 is a foam obtained by adding a complex compound of heptafluoro-2-iodopropane and tetramethylhexamethylenediamine. In this case, the immobilization rate of carbon dioxide was high, and it was found that 90% or more of carbon dioxide was immobilized by gas analysis one day after the production. Since the foam has a low density and is improved, it is considered that the complex compound acts as a urethane reaction catalyst. In addition, it can be considered that the complex compound produces free iodine and acts as an immobilized catalyst. Sample No. In 5-3 and 5-4, the thermal conductivity decreased further after a lapse of one month. As an example of using the heat insulating resin foam according to the present invention, a refrigerator box is shown in FIG.
It is configured by combining an outer box 1 made of metal and an inner box 3 made of hard resin. The hard resin inner box 3 is a thermoplastic resin because of its moldability. It is desirable that this thermoplastic resin not be attacked by the polyurethane foam insulation 2 of the present invention.
Resins and the like are suitable.

[0096]

The foaming agent used in the present invention comprises at least one of a fluorinated iodohydrocarbon, a perfluoroalkene and a hydrogen-containing fluorinated morpholine derivative. This foaming agent has a low gas thermal conductivity and is not inferior to the designated CFC HCFC141b, has extremely low environmental destructive potential such as ozone depletion potential (ODP) and global warming potential (GWP), and has the same performance as a conventional foam. A resin foam having excellent heat insulation is provided. In particular, since fluorinated iodohydrocarbon has flame retardancy and self-extinguishing property, it can be used as a safe mixed foaming agent by mixing it with a foaming agent having high risk of explosion such as hydrocarbon. .

If a carbonate compound, an ester, or an epoxide is added to the above-mentioned foaming agent, the foamability is improved. By adding a reducing agent or an oxygen absorbent, the performance of the foam can be maintained for a long time. The above-mentioned foaming agent is a mixture of water, a ketone, an ether, an ester, and a hydrocarbon to form a mixed foaming agent, whereby the premix is modified, the foaming property is improved, and the bubbles are uniformly miniaturized. It gives a high performance resin foam.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a heat insulating box body filled with a rigid polyurethane foam according to the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Suzuki, 1006 Kadoma, Kadoma City, Osaka Prefecture, Matsushita Electric Industrial Co., Ltd. (72) Yoshio Kishimoto, 1006 Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.

Claims (27)

[Claims] 1. A foamed resin composition having closed cells, wherein fluorinated iodohydrocarbon is contained in the closed cells.
A heat insulating resin foam comprising a gas of a foaming agent composed of at least one compound selected from the group consisting of a perfluoroalkene and a hydrogen-containing fluorinated morpholine derivative. 2. The heat insulating resin foam according to claim 1, wherein the foaming agent is one of a fluorinated iodohydrocarbon, and a perfluoroalkene and a hydrogen-containing fluorinated morpholine derivative. 3. The heat insulating resin foam according to claim 1, wherein the foamed resin composition contains a reducing agent. 4. The heat insulating resin foam according to claim 1, wherein the foamed resin composition contains an oxygen absorbent. 5. A heat insulating resin foam comprising a complex compound of a fluorinated iodohydrocarbon and an amine having a non-conjugated bond or an ammonium salt or a quaternary ammonium salt. 6. The heat insulating resin foam according to claim 1, wherein the fluorinated iodohydrocarbon has a carbon number of 4 or less and a boiling point of 65 ° C. or less. 7. The fluorinated iodohydrocarbons are iodotrifluoromethane, iodopentafluoroethane, 1
-Iodoheptafluoropropane, 2-iodoheptafluoropropane, iodo-1,1,2,2-tetrafluoroethane, 2-iodo-1,1,1-trifluoroethane, iodotrifluoroethylene, 1 7. At least one selected from the group consisting of iodo-1,1,2,3,3,3-hexafluoropropane, and 2-iodononafluoro-t-butane.
The heat-insulating resin foam according to. 8. A perfluoroalkene is hexafluoropropene dimer, perfluoro-2-pentene,
The heat insulating resin foam according to claim 1, which is at least one selected from the group consisting of (perfluorobutyl) ethylene, (perfluoropropyl) ethylene, and octafluorocyclopentane. 9. A hydrogen-containing fluorinated morpholine derivative,
The heat insulating resin foam according to claim 1, which is at least one selected from the group consisting of monohydroperfluoromorpholine and monohydroperfluoromethylmorpholine. 10. The closed cell further contains at least one hydrocarbon selected from the group consisting of pentane, isopentane and cyclopentane.
The heat insulating resin foam according to 2 or 5. 11. The heat insulating resin foam according to claim 10, wherein the content of the hydrocarbon is 45 to 96 mol%. 12. A foaming agent, a polyol, a polyisocyanate, a urethane reaction catalyst and a foam stabilizer, which comprises at least one compound selected from the group consisting of fluorinated iodohydrocarbons, perfluoroalkenes and hydrogen-containing fluorinated morpholine derivatives. A method for producing a heat insulating resin foam, which comprises foaming and molding by mixing a resin raw material composition containing an agent. 13. The method for producing a heat insulating resin foam according to claim 12, wherein the foaming agent is a fluorinated iodohydrocarbon, or a perfluoroalkene and a hydrogen-containing fluorinated morpholine derivative. 14. The method for producing a heat insulating resin foam according to claim 12, further comprising water as a foaming agent. 15. A boiling point of 100 in the raw material of the resin composition.
The method for producing a heat insulating resin foam according to claim 12, which contains at least one of a carbonate compound, an ester, and an epoxide at a temperature of not less than 0 ° C. 16. The resin raw material composition is formed by mixing a polyisocyanate emulsion obtained by dispersing a reducing agent together with a surfactant in a polyisocyanate composition with a polyol. 13. The method for producing a heat insulating resin foam according to 13. 17. The blowing agent comprises at least a fluorinated iodohydrocarbon, and the polyol comprises at least 30.
The method for producing a heat insulating resin foam according to claim 12 or 13, which contains wt% of a non-amine-based polyol. 18. The heat insulating resin foam according to claim 12, wherein the resin raw material composition contains, as a foaming nucleus, a salt soluble in a primary alcohol or a secondary alcohol having 3 or less carbon atoms. Production method. 19. Foaming by mixing a resin composition raw material containing a complex compound of a fluorinated iodohydrocarbon and an amine having a non-conjugated bond, an ammonium salt or a quaternary ammonium salt, a polyol, and a polyisocyanate. A method for producing a heat insulating resin foam, which comprises molding. 20. The heat insulating resin according to claim 19, wherein fluorinated iodohydrocarbon is separated from the complex compound by the heat of reaction between the polyol and polyisocyanate, and the fluorinated iodohydrocarbon acts as a foaming agent. Method for producing foam. 21. The resin composition raw material further contains at least one urethane reaction catalyst selected from the group consisting of an organic tin compound, a metal salt of an organic acid, an aromatic amine, and an organic phosphorus compound. A method for producing a heat insulating resin foam. 22. The heat insulation according to claim 19, wherein the resin composition raw material further contains water in an amount up to an equimolar amount with the complex compound and not more than 10 parts by weight with respect to 100 parts by weight of the polyol component. For producing a flexible resin foam. 23. A foam produced by the resin raw material composition containing an epoxide and a carbon dioxide-immobilized catalyst, wherein carbon dioxide produced during the foaming step reacts with the epoxide to form a carbonate compound. The method for producing a heat-insulating resin foam according to claim 12, 13 or 19, which has a step of reducing the pressure inside the bubbles. 24. The resin raw material composition comprises a polyisocyanate composition in which a fluorinated iodohydrocarbon and the carbon dioxide-immobilized catalyst are mixed, a polyol, a urethane reaction catalyst, the epoxide, and a foam stabilizer. The method for producing a heat insulating resin foam according to claim 23, which is formed by mixing with a mix. 25. The resin raw material composition contains a complex compound of the carbon dioxide-immobilized catalyst and a fluorinated iodohydrocarbon, and the complex compound is decomposed by the heat of reaction between the polyol and the polyisocyanate to produce fluorine. 24. The heat insulation according to claim 23, comprising a step of producing a fluorinated iodohydrocarbon and a carbon dioxide-immobilized catalyst, wherein the produced carbon dioxide-immobilized catalyst acts on the reaction between the epoxide and the carbon dioxide produced during the foaming step. For producing a flexible resin foam. 26. The foaming agent further comprises at least one hydrocarbon selected from the group consisting of pentane, isopentane and cyclopentane.
Alternatively, the method for producing a heat insulating resin foam according to Item 19. 27. The method for producing a heat insulating resin foam according to claim 26, wherein the content of the hydrocarbon is 45 to 96 mol%.