JPH08145279A - Heat insulation foaming body and manufacture thereof - Google Patents

Abstract

PURPOSE: To provide a heat insulation foaming body excellent in its foaming property by use of substitute fluorocarbon foaming agent. CONSTITUTION: A heat insulation foaming body is made of a urethane foaming resin composite and including metalocene. To manufacture this foaming body, a polyore composite, isocianate composite and a foaming agent which is obtained by dispersing or dissolving metallocene of foaming nucleus agent are mixed and foamed to provide a heat insulator of which heat insulation property is featured by foaming agent gas. This foaming body includes, in air bubbles of foaming resin composite of urethane, metallocene in which cyclopendadiene of foaming agent is fixed. A metallocene reactive metal composite for forming metallocene through reaction with cyclopentadiene used as the foaming agent is mixed and foamed to provide a heat insulator having pressure reduced air bubbles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat insulating foam made of a urethane foam resin composition used for a cold storage device or a cold storage facility such as a refrigerator or a freezer, or a heat insulating member for a house, and a method for producing the same. .

[0002]

2. Description of the Related Art Conventionally, foamed resin compositions such as urethane foam and styrene foam have been mainly used as heat insulators used in refrigerators, freezers and the like. In particular, urethane resins are widely used because they can be foamed in situ. Many of these make up a closed cell body,
As a foaming agent for forming cells, CFCs having good foaming suitability and low thermal conductivity have been used, and excellent heat insulating foams have been constructed. However, the thermal insulation foam using specific CFCs with low thermal conductivity such as trichloromonofluoromethane (CFC11) has been regulated by global environmental problems such as ozone layer depletion and global warming, and thus has been designated as an alternative CFC. The investigation of foaming agents is ongoing. As an alternative CFC blowing agent, a specified CFC such as 1,1-dichloro-1-fluoroethane (HCFC141b) is used (for example, JP-A-5-222146). As for this designated CFC, there is still a possibility of ozone layer depletion, and the issue of global warming remains, so use restrictions are planned.

Therefore, the development of a foaming agent that does not cause ozone layer depletion is underway. Among them, hydrocarbon compounds have also been investigated as alternative freon blowing agents, and cyclopentane and the like have been proposed (for example, JP-A-3-152160 and JP-A-3-54231). Further, blowing agents for fluorinated compounds such as partially fluorinated hydrocarbon compounds and perfluorinated carbon compounds have also been proposed (for example, JP-A-5-247251 and JP-A-5-287109). . In addition, for the purpose of reducing the amount of foaming agents such as CFCs, and for the purpose of improving foam strength by the urea bond formed by carbon dioxide being generated by the reaction of isocyanate, which is the raw material of urethane resin, and water, and foaming. A heat insulator made of a urethane foam resin that also uses water as an agent is used. In this case, in order to improve the heat insulating property of the foaming agent, zeolite adsorbed by a thermal equilibrium reaction may be mixed in for the purpose of reducing carbon dioxide in the closed cells of the urethane resin (for example, JP-A-3- 292113 and U.S. Pat. No. 4,882,363).

Further, as a heat insulating material having good heat insulating performance, there is a vacuum heat insulating material. This is because the heat insulator is sealed in a container for holding a vacuum, and the inside of the container is evacuated to further reduce the thermal conductivity, and has an extremely high heat insulating property. As the structure and material of this vacuum heat insulator, inorganic fine particulate heat-insulating powder such as pearlite and silica, urethane foam of open cell body, in a container with high gas barrier property such as metal / plastic slaminate film and plastic multilayer film. Alternatively, many proposals have been made in which a honeycomb structure or the like is put together with a gas adsorbent as a core material and vacuum-sealed (for example, Japanese Unexamined Patent Application Publication No. Sho.
7-133870, JP-A-63-21475 and JP-A-2-772293). Furthermore, by using a foaming agent of a reactive monomer, the foaming agent is reacted in the bubbles of a heat-insulating foam made of closed-cell body to oligomerize or polymerize at least dimerization, and the inside of the bubbles is decompressed and insulated. A method for improving the property has been proposed (for example, Japanese Patent Laid-Open No. 6-41341). As an example,
The dimerization reaction of cyclopentadiene to dicyclopentadiene is shown. In that case, the degree of pressure reduction in the bubbles is
Since dicyclopentadiene is a liquid at room temperature and has a saturated vapor pressure, the internal pressure is said to be about 10 mmHg.

[0005]

CFC-based blowing agents have not solved the problems of ozone layer depletion and environmental destruction such as global warming. On the other hand, a hydrocarbon compound without such a problem is
There is a problem that it is flammable and has a risk of explosion and the like, and it has a high thermal conductivity as compared with fluorocarbons, so that only a foam having a slightly poor heat insulating property can be obtained. Further, a partially fluorinated carbon-hydrogen compound having a relatively good heat insulating property and flame retardance has a problem that it is poor in compatibility with a resin raw material and it is difficult to form a high quality foam. Therefore, these hydrocarbon compounds are used as additives for controlling the bubbles of other foaming agents, a large amount of water as an auxiliary foaming agent, silica, alumina or other inorganic fine particles as a foam nucleating agent, organic powder such as starch, etc. Although it is used as a mixture with the above insoluble dispersant, the problems of improving the physical properties of the foam and improving the heat insulating property still remain.

[0006] Further, since the vacuum heat insulator having a very excellent heat insulating property has a well-defined heat insulating property, it has a fixed shape. Therefore, a box having various shapes such as a foam heat insulator made by in-situ foaming of urethane. It is not a simple method that can be arbitrarily injected into the body, and a step of attaching a vacuum heat insulator to the box was necessary. Adiabatic foams that use a reactive monomer as a foaming agent to carry out the dimerization reaction of the foaming agent in air bubbles do not have sufficient vacuum because the reaction product has a saturated vapor pressure Was insufficient. Furthermore, when water used to modify the foam such as foaming reactivity, strength, and fluidity for filling into a container is used together, sufficient thermal insulation is achieved due to the effect of carbon dioxide generated. There was a problem that was not obtained.

In view of the above, it is an object of the present invention to improve the physical properties of foam and to provide a heat insulating foam having excellent heat insulating properties. The present invention also does not require a depressurizing vacuuming process or panel pasting process using a conventional vacuum pump or the like,
An object of the present invention is to provide a heat insulating foam made of a urethane foam resin composition which can be produced by in-situ foaming and which can obtain excellent heat insulating property by reducing the pressure inside the cells.

[0008]

The heat insulating foam of the present invention comprises:
It is composed of a urethane foam resin composition formed by mixing a polyol composition, an isocyanate composition, and a foaming agent, and contains a metallocene. Further, the heat insulating foam of the present invention contains metallocene in which cyclopentadiene as a foaming agent is immobilized in the cells of the urethane foam resin composition. Further, a compound having carbon dioxide immobilized therein is contained in the bubbles. Here, the metallocene is preferably ferrocene.

In the method for producing a heat insulating foam of the present invention, the urethane composition, the isocyanate composition, and the foaming agent in which the metallocene as the foaming nucleating agent is dispersed or dissolved are mixed and foamed to give a urethane foamed resin. It forms a heat insulating foam made of the composition. As the foaming agent used here,
It is preferable to use one containing any one of a cyclic hydrocarbon compound, a cyclic ether compound and a highly fluorinated hydrocarbon compound. In particular, cyclopentane, furan, trifluoropropylene oxide, tetrafluoroethylene (HFC
134a), iodopentafluoropropane are preferred.

The method for producing a heat insulating foam of the present invention is
Polyurethane composition, isocyanate composition, blowing agent cyclopentadiene, and urethane foam resin produced by mixing and foaming a metallocene-reactive metal-containing composition that reacts with cyclopentadiene to form metallocene The method includes a step of solidifying cyclopentadiene as metallocene by reacting cyclopentadiene with the metallocene-reactive metal-containing composition in the bubbles of the composition, and reducing the pressure in the bubbles. Further, the method for producing a heat insulating foam of the present invention is a metallocene-reactive metal-containing composition for forming a metallocene by reacting with a polyol composition, an isocyanate composition, a cyclopentadiene as a foaming agent and water, and cyclopentadiene. Substance and a solidification aid for solidifying carbon dioxide are mixed and foamed to produce cyclopentadiene by the reaction between cyclopentadiene and the metallocene-reactive metal-containing composition in the bubbles of the urethane foam resin composition produced. Is solidified as a metallocene, and carbon dioxide generated by the urea bonding reaction between the water and the isocyanate composition is solidified by the solidification aid to reduce the pressure inside the bubbles.

In the above-mentioned production method, cyclopentadiene is likely to dimerize at room temperature, and therefore cyclopentadiene is preferably mixed therewith just before mixing the polyol composition and the isocyanate composition. Further, in these production methods, the metallocene-reactive metal-containing composition is composed of a metal halide and a basic compound, in particular, the metallocene compound is ferrocene, the metallocene-reactive metal-containing composition is an iron dichloride compound. And an amine compound or a metal hydroxide. The solidification aid for solidifying carbon dioxide may be any of a metal oxide, a metal hydroxide, a combination of an epoxy compound and a copolymerization catalyst, and a combination of an epoxy compound and a cyclization reaction catalyst. It is suitable because carbon dioxide can be solidified efficiently.

[0012]

The present invention has the above-mentioned constitution, and the metallocene compound plays the following role in the process of forming the heat insulating foam made of the urethane foam resin composition. First, when the polyol composition, the isocyanate composition and the foaming agent are mixed, the metallocene acts as a foam nucleating agent in urethane foaming. Second, when cyclopentadiene (boiling point: about 42 ° C.) is used as a foaming agent, cyclopentadiene reacts with the metallocene-reactive metal-containing composition in the bubbles of the urethane foam resin composition to form a metallocene of the metal complex. By forming and solidifying the above, it acts as a reaction depressurizing agent that depressurizes the inside of the bubbles.

First, the effect as foam nuclei is considered as follows. It has been already known to add foam nuclei as a method for improving foam physical properties such as foam density, cell diameter, and strength, and reducing thermal conductivity to improve heat insulation. As the foam nucleating agent, fine particles of an inorganic compound, fine powder of an organic compound, fine particles of a polymer or the like are used.
For example, fine particles of silica, alumina, magnesium oxide, etc., starch, fine particles of polyethylene, etc., which are insoluble in a foaming agent, a polyol composition, etc., are used by being dispersed therein. Generally, it is used in the order of several tens of nm to submicron and micron. However, when they are dispersed, aggregation of fine particles is likely to occur, which is originally several tens nm.
In practice, even the primary particles described above tend to exist as large particles of submicron to micron order due to secondary aggregation and the like. Therefore, when it works as a foam nucleus,
Since the number of particles is small, it is easy to generate bubbles with a large bubble diameter.
It is difficult to achieve the desired effect. Further, in order to obtain an excellent effect, it is necessary to add a large amount of foam nucleating agent. On the other hand, when metallocene is used as a foam nucleating agent,
In the case of a foaming agent that dissolves metallocene, when the dissolved concentration of metallocene increases during the foaming process, a small amount of metallocene precipitates to form small foam nuclei. Also, when the foaming agent is premixed with the polyol composition,
The metallocene has a low solubility and is precipitated, but since it has a high affinity, it disperses in a state close to molecular dispersion to form a foam nucleus. Therefore, the number of nuclei is large and a good effect is obtained. Furthermore, even when a foaming agent that does not dissolve metallocene is used, metallocene is considered to be in a state close to molecular dispersion because of its relatively high affinity with organic solvents, and a good effect is obtained. .

Next, the effect as a reaction depressurizing agent will be described. Cyclopentadiene easily dimerizes into dicyclopentadiene at room temperature. Therefore, when cyclopentadiene is used as a foaming agent, it is possible to form a foam in which the pressure inside the cells is reduced by a dimerization reaction. However, the produced dicyclopentadiene (boiling point about 64 ° C / 1
4 mmHg, melting point −32 ° C.) has a vapor pressure of several mmHg at room temperature. Therefore, it is not possible to reduce the pressure in the bubbles to a pressure of 1 mmHg or less at which the effect of vacuum heat insulation is sufficiently obtained. Further, in order to improve the foamability, when other gas, for example, carbon dioxide generated by the reaction of water and isocyanate is present in the bubbles, the contribution of carbon dioxide having high thermal conductivity as the depressurization progresses. On the contrary, the heat insulating property deteriorates because of the high temperature, and it is not possible to use water, which can improve the foaming performance, as a foaming agent. Therefore, in the present invention, cyclopentadiene is used as the foaming agent, and the gas of cyclopentadiene present in the bubbles of the urethane foaming resin composition produced by foaming is solidified as metallocene. As a result, it is possible to reduce the pressure inside the bubbles to the vapor pressure of dicyclopentadiene or less, and it is also possible to obtain the performance as vacuum heat insulation. This metallocene reaction is shown in Formula (1) and Formula (2) using a divalent metal compound as an example.

[0015]

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Here, M is a divalent metal element, X is a halogen element, and n is an integer. Cyclopentadiene reacts with a metal halide in the presence of a basic compound to form a metallocene. In the reaction of the formula (2), by adding potassium hydroxide in excess, water can be captured as a hydrate. Further, in the urethane reaction, water generated by the reaction of the formula (2) can be removed by reacting with isocyanate. Further, even when a hydrate of a metal halide is used in the reaction of the formula (1), water is desorbed due to the heat generated by the urethane reaction and reacts with the isocyanate to be removed.
A similar reaction proceeds. This metallocene is solid,
It has a melting point of 100 ° C or higher depending on the metal forming the complex salt. For example, ferrocene produced when using an iron dichloride compound has a melting point of about 172 ° C., is particularly thermally stable among many metallocenes, and does not decompose even when heated to 470 ° C. The metallocene-reactive metal-containing composition is composed of a metal halide and a basic compound.

Further, in the present invention, water can be used in combination with cyclopentadiene as a foaming agent. Although carbon dioxide generated by the reaction between water and isocyanate is filled in the bubbles, it is possible to react the carbon dioxide with a solidification aid for solidifying the carbon dioxide in the bubbles to solidify them. The solidification aid may be at least a metal oxide, a metal hydroxide, a combination of an epoxy compound and a copolymerization catalyst, or a combination of an epoxy compound and a cyclization reaction catalyst. It is suitable because it is efficiently converted. For example, in the case where the metal oxide and the metal hydroxide are respectively calcium, for example, formula (3)-
As in (6), metal carbonate is formed to solidify carbon dioxide.

[0018]

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The solidification reaction using the epoxy compound and the copolymerization catalyst, and the epoxy compound and the cyclization reaction catalyst,
Carbon dioxide is solidified as in equations (7) and (8), respectively. In the former, alternating polymerization is performed to form a polycarbonate, and in the latter, a cyclic carbonate is formed.

[0020]

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In equations (7) and (8), R ₁ ,
R ₂ , R ₃ and R ₄ are hydrogen atoms or substituents. In the above formula, the epoxide compound is shown as a three-membered ring ether, but the same reaction proceeds even if it has four or more membered rings.

[0022]

EXAMPLES Next, the present invention will be described in more detail with reference to examples. An example of the first heat insulating foam of the present invention is shown in FIGS. 1 and 2. In a container 6 composed of an outer box 1 and an inner box 2, a urethane foam resin composition 3 composed of closed cells is formed. The urethane foam resin composition 3 contains the metallocene 4 in the vicinity of the bubbles 5, and the bubbles are filled with the foaming agent gas. When actually used, the heat-insulating foam is often used in a container that gives a shape as in this example. A polyol composition, an isocyanate composition,
By mixing with the foaming agent in which the metallocene compound 4 which is a foaming nucleating agent is dispersed or dissolved and injecting it into the container 6, a urethane forming reaction and vaporization of the foaming agent occur in the container 6, and the urethane foamed resin composition 3 Is formed. During this mixing / foaming process, the metallocene dispersed or dissolved in the foaming agent precipitates in a molecularly dispersed state as the concentration changes and forms extremely fine foam nuclei, so the density is low, the cell diameter is small, and the foam A strong insulating foam is formed. Along with that, the thermal conductivity of the resin component and the thermal conductivity due to radiation decrease, so the gas thermal conductivity of the foaming agent is fully utilized, and the thermal insulation with low foam thermal conductivity and excellent heat insulation is achieved. A foam is obtained.

As the foaming agent used here, a general one such as CFC can be effective. However, as a result of various investigations by the present inventors, such as a straight chain hydrocarbon compound and a branched hydrocarbon compound, a cyclic hydrocarbon is obtained. The effect was obtained when the compound, the cyclic ether compound, or the highly fluorinated hydrocarbon compound was contained. In particular, it was effective when cyclopentane, furan, trifluoropropylene oxide, tetrafluoroethylene (HFC134a), 1- or 2-iodopentafluoropropane was contained. The effect is obtained when the amount of the metallocene, which is a foam nucleating agent, is about 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyol composition. Preferably 0.5 to 5 parts by weight are used. The obtained foam has excellent physical properties such as a density of 0.035 kg / cm ³ or less, a cell diameter of 200 μm or less, and a foam strength of 1 kg / cm ² or more. It was an excellent insulating foam that was fully demonstrated.

An example of the second heat insulating foam of the present invention is shown in FIG. The urethane foamed resin composition 3 composed of closed cells formed in the container 6 has decompressed cells 8 in which cyclopentadiene, which is a foaming agent, is a metallocene-reactive metal-containing composition. It contains metallocene 7 solidified by reaction and a reaction product. A polyol composition, an isocyanate composition, cyclopentadiene as a foaming agent,
By mixing and injecting the metallocene-reactive metal-containing composition into the container 6, the urethane forming reaction and the foaming of the foaming agent occur in the container 6, and the urethane foamed resin composition 3 is formed. At the initial stage of completion of foaming, the gas of cyclopentadiene is filled in the bubbles 8, but reacts with the metallocene-reactive metal-containing composition to form metallocene 7 which solidifies to reduce the pressure in the bubbles 8. Metallocene is a solid unlike dimerized dicyclopentadiene,
The pressure in the bubble 8 is reduced to 1 mmHg or less. Therefore, an excellent vacuum insulating foam is formed.

The metallocene-reactive metal-containing composition is composed of a metal halide and a basic compound. As the divalent metal element forming the metallocene compound, iron, titanium,
Vanadium, chromium, manganese, cobalt, nickel,
Ruthenium and the like are used, and the names of ferrocene, titanocene, vanazinocene, chromocene, manganocene, cobaltocene, nickelocene, and ruthenocene are used, respectively. It is not limited to these metals. As the metal halide X, halogens such as fluorine, chlorine, bromine and iodine are used, but chloride is mainly preferable. The metal halide may be a hydrate having water of crystallization. Further, as the basic compound, an amine compound or a metal hydroxide is suitable. Amine compounds are primary and 2
Grade and tertiary amines are used and also act as catalysts for urethane reactions. Substituents include, but are not limited to, methyl, ethyl, propyl, butyl groups and the like.
As the metal hydroxide, alkali metal hydroxides of lithium, sodium and potassium can be applied.

Next, an example of the third heat insulating foam of the present invention will be described. The closed-cell urethane foam resin composition 3 formed in the container 6 in the same manner as the second heat-insulating foam has decompressed cells 8 in which cyclopentadiene as a foaming agent is metallocene. Metallocene 7 and a reaction product solidified by reacting with a metal-reactive metal-containing composition, and carbon dioxide generated by the reaction of water as a foaming agent with an isocyanate and a solidification aid to solidify a compound. Contains. In the case of this example, the gas after the foaming is filled with cyclopentadiene gas and carbon dioxide. Cyclopentadiene solidifies into metallocene in the same manner as above. Carbon dioxide is a metal oxide that is a solidification aid,
A metal hydroxide, an epoxy compound and a copolymerization catalyst, or an epoxy compound and a cyclization reaction catalyst are solidified to reduce the pressure inside the bubbles. The pressure inside the bubble is 1 mmHg
When the pressure is reduced to the level below, excellent heat insulation is exhibited, and when water reacts with isocyanate to generate carbon dioxide, a urea-bonded resin is formed and crosslinked, so that a heat-insulating foam having excellent strength is obtained.

As a metal salt of a metal oxide or a metal hydroxide which is a solidification aid for carbon dioxide, a salt containing an alkaline earth metal such as a calcium salt, a barium salt or a magnesium salt is suitable. Since these reactions are promoted when a free amino group is present, it is preferable to have a lysine residue or an ammonium halide or ammonium phosphate functional group. Furthermore, as the epoxy compound used as a solidification aid for carbon dioxide, the epoxy group is 1
A compound containing one or two, or an oxetane derivative or a tetrahydrofuran derivative is preferable.
Among the epoxide compounds having one epoxy group, those having a boiling point of about 60 ° C. or lower also function as a foaming agent.
Examples of such compounds include ethylene oxide (11 ° C.), propylene oxide (34 ° C.), 1,2-
Epoxy butane (63 ° C), cis 2,3-epoxy butane (60 ° C), trans 2,3-epoxy butane (54
C.) and butadiene monooxide (65.degree. C.). However, the values in parentheses are the boiling points of the compounds. As the other epoxide compound having one epoxy group, for example, alkylene oxide compounds such as epoxyhexane, epoxyoctane, epoxydecane, epoxydodecane, epoxyhexadecane, and epoxyoctadecane are suitable. Further, compounds having an epoxy group and a double bond unsaturated group such as epoxyhexene and epoxyoctene, compounds having a glycidyl group such as glycidyl methyl ether, glycidyl isopropyl ether, glycidyl acrylate and phenyl glycidyl ether, epoxypropylbenzene, styrene. Aromatic epoxide compounds such as oxides can also be used. Also,
Compounds such as diepoxybutane and diepoxyoctane having two epoxy groups, oligomers having various epoxy groups at both ends, and oxetane (boiling point 50 ° C)
And its derivatives can also be used. Since some of these epoxide compounds may react with the polyol, they may be combined with the foamed resin composition. Further, when a brominated epoxide compound is used, it is possible to make the foamed heat insulating material flame-retardant.

As the copolymerization catalyst, a metal compound such as zinc, cobalt, aluminum or tin is suitable. In particular, a mixture of an organic zinc compound and a compound having a divalent or higher active hydrogen, which is composed of a zinc compound, a metal oxide-supported organic zinc compound, a zinc acetate salt, a reaction mixture of zinc hydroxide and an aliphatic dicarboxylic acid, or Zinc halides carrying metal oxides are suitable as copolymerization catalysts. Suitable organic zinc compounds are dialkyl zinc such as diethyl zinc, and compounds having active hydrogen with a valency of 2 or higher are water, primary amines, dihydric alcohols, aromatic dicarboxylic acids, aromatic hydroxycarboxylic acids and the like. There is. Silicon oxide, aluminum oxide, titanium oxide, etc. are used as the metal oxide carrying the zinc compound,
Further, a metal hydroxide such as magnesium oxide can also be used. Further, the copolymerization reaction of carbon dioxide and an epoxide compound occurs even when all the raw materials are mixed to form a foamed resin, but specifically, the catalytic activity can be improved by previously mixing the epoxide compound and the copolymerization catalyst. It is preferable because the copolymerization rate becomes high and the copolymerization proceeds at a high yield.

As the addition reaction catalyst, a phosphonium salt,
A composition comprising an onium compound such as an ammonium salt, a sulfonium salt, an oxonium salt, an arsonium salt, a stibonium salt, a selenonium salt, an iodonium salt or a stannonium salt is used, and particularly, a quaternary onium salt and an organometallic halide, or The reaction yield of the mixed catalyst of the quaternary onium salt and the metal halide is high.
Suitable onium compounds are tetraalkylphosphonium halides, tetraalkylammonium halides, etc., and tetrabutylphosphonium iodide, tetrabutylphosphonium bromide, tetrabutylammonium iodide, and tetrabutylammonium bromide have high catalytic activity. can get. A tin compound is suitable as the organic metal halide, and tributyltin iodide, tributyltin bromide, tributyltin chloride, trimethyltin iodide, triphenyltin iodide, or the like can be used. further,
A zinc compound is suitable as the metal halide, and zinc chloride, zinc bromide or the like can be used. The mixing ratio of the mixed catalyst can be applied in the range of 1/10 to 5 times the organometallic halide or the metal halide with respect to the onium compound. And, the amount of these catalysts is 1/10 to 1/50 with respect to the epoxide compound, and sufficient activity can be exhibited. Then, the reaction between carbon dioxide and the epoxide compound occurs even when all the raw materials are mixed to form a foamed resin, but specifically, by previously mixing the epoxide compound and the addition reaction catalyst, the catalytic activity becomes high. It is preferable because the addition reaction proceeds at a high yield.

In the present invention, a urethane resin is used as the heat insulating foam, but various resins such as phenol resin, nylon resin and olefin resin forming other foams can be applied. Particularly, polystyrene other than urethane resin is used. Similar excellent heat insulating properties can be obtained with resins and vinylidene chloride resins. As a raw material of the urethane resin, generally, a polyol composition, a urethane reaction catalyst for accelerating the reaction, a foam stabilizer, and a premix in which a foaming agent is mainly mixed, and an isocyanate composition are used. By mixing these two liquids, the foaming agent is foamed by the reaction heat when the urethane bond is mainly formed by the reaction between the hydroxyl group of the polyol and the isocyanate to form a heat insulating foam. . If necessary, an antioxidant, a flame retardant, a filler, a cross-linking agent, etc. are used in the premix. It should be noted that cyclopentadiene used as a foaming agent is easily prepared at room temperature.
Since it is easy to quantify into dicyclopentadiene, it is desirable to mix the polyol composition with the isocyanate composition at the same time. When pre-mixed with the polyol composition, the dimerization reaction tends to be delayed because the compatibility with the polyol is relatively good, so the premixed raw materials can be stored for a short period of time. Is.

As the polyol composition, a high molecular weight compound containing at least two reactive hydrogen atoms is generally used, and a polyether polyol or polyester polyol having a hydroxyl value of 200 to 600 mgKOH / g is preferably used. The isocyanate composition is a compound containing at least two isocyanate groups, such as tolylene diisocyanate, crude diphenylmethane diisocyanate, or an isocyanate mixture or organic polyisocyanate resin based on these. The amine equivalent of 100 to 300 is generally used.
As the foam stabilizer, an organic silicone-based surfactant,
Although there are fatty acid metal salts, aliphatic sulfonic acid metal salts, paraffin oil, and the like, organic silicone surfactants are preferably used. As the urethane reaction catalyst, organotin compounds, organolead compounds, highly basic amine catalysts and the like are used, but amine catalysts are preferably used.

[Example 1] Hydroxyl value 449 mgKOH /
100 parts by weight of polyether polyol of 3 g, 3 parts by weight of a silicone type foam stabilizer and 2 parts by weight of an amine type catalyst were mixed. Next, 3 parts by weight of ferrocene, which is a foam nucleating agent, was dispersed in 17 parts by weight of cyclopentane as a foaming agent, and 1 part by weight of this foaming agent and water were added to the above mixture and mixed sufficiently. Next, 138 parts by weight of crude diphenylmethane diisocyanate-based isocyanate having an amine equivalent of 134 was mixed with this mixed solution at a stirring speed of 4500 rpm for 5 seconds, and then poured into a container and subjected to a foaming reaction to obtain a heat-insulating foam of closed cells. .
After the container was cured at 45 ° C., it was cut into a shape of about 20 cm × 20 cm × 2 cm for evaluating the physical properties of the foam. [Comparative Example 1] A heat insulating foam was produced in the same manner as in Example 1 except that ferrocene which was a foam nucleating agent was not added.

Example 2 10.8 parts by weight of furan (mixing molar ratio 65%) and perfluoromethylmorpholine 2
A heat insulating foam was produced in the same manner as in Example 1 except that 0.8 part by weight of titanocene as a foam nucleating agent was dissolved in 5.5 parts by weight (35% by mole) of a mixed foaming agent. . [Comparative Example 2] A heat insulating foam was produced in the same manner as in Example 2 except that the foam nucleating agent titanocene was not used. [Example 3] 5 parts by weight of ferrocene as a foam nucleating agent was added to 2 parts.
-Dispersed in 30 parts by weight of iodopentafluoropropane /
A heat insulating foam was produced in the same manner as in Example 1 except that the heat insulating foam was dissolved. [Comparative Example 3] 5 parts by weight of silica fine particles were used as a foam nucleating agent.
A heat insulating foam was produced in the same manner as in Example 1 except that 30 parts by weight of 2-iodopentafluoropropane was dispersed. [Comparative Example 4] A heat insulating foam was produced in the same manner as in Example 3 except that ferrocene which was a foam nucleating agent was not used. [Example 4] 3 parts by weight of nickelocene was used as a foam nucleating agent.
A heat insulating foam was produced in the same manner as in Example 1 except that 26 parts by weight of 1,1,1,4,4,4-hexafluorobutane was dispersed / dissolved.

Table 1 shows the results of evaluation of foam physical properties of the heat insulating foams of the above Examples and Comparative Examples. The thermal conductivity was measured at an average temperature of 24 ° C. As is clear from Table 1, when metallocene is used as the foam nucleating agent, the foam physical properties such as density and cell diameter are improved, and a heat-insulating foam with good thermal insulation and reduced thermal conductivity can be obtained. Further, the foam strength also shows a sufficient value.

[0035]

[Table 1]

[Example 5] Hydroxyl value 449 mgKOH /
g of 100 parts by weight of polyether polyol, 3 parts by weight of silicone-based foam stabilizer, and 3 parts by weight of amine-based catalyst, 22 parts by weight of cyclopentadiene as a foaming agent, and dichloride as a metallocene-reactive metal-containing composition. 21 parts by weight of iron, 22 parts by weight of diethylamine, and 1 equivalent of amine
125 parts of 34 crude diphenylmethane diisocyanate-based isocyanates were mixed at a stirring speed of 4500 rpm for 5 seconds, and then poured into a container and subjected to a foaming reaction to obtain a heat-insulating foam of closed cells. After curing the entire container at 45 ℃, about 20 cm × 20 cm × 2 to evaluate the physical properties of the foam
It was cut into a shape of cm. [Comparative Example 5] A heat insulating foam was produced in the same manner as in Example 5 except that the metallocene-reactive metal-containing composition was not added.

Example 6 Hydroxyl value 449 mg KOH /
8 parts by weight of cyclopentadiene as a blowing agent in a mixed solution of 100 parts by weight of polyether polyol, 4 parts by weight of a silicone-based foam stabilizer, and 0.5 parts by weight of an amine catalyst.
13 parts by weight of iron dichloride tetrahydrate and 28 parts by weight of potassium hydroxide, 3 parts by weight of water as a metallocene-reactive metal-containing composition, and 25 parts by weight of phenyl glycidyl ether and tetrabutylammonium as a solidification aid for carbon dioxide. 1 part by weight of bromide, 1 part by weight of zinc chloride, and 172 parts of crude diphenylmethane diisocyanate-type isocyanate having an amine equivalent of 134 were mixed at a stirring speed of 4500 rpm for 5 seconds, and then poured into a container to cause a foaming reaction to obtain a heat insulating foam. It was After the container was cured at 45 ° C., it was cut into a shape of about 20 cm × 20 cm × 2 cm for evaluating the physical properties of the foam.

The foam physical properties of the foams of Examples 5 and 6 and Comparative Example 5 were evaluated, and the results are shown in Table 1. As shown in Table 2, when the foaming agent is solidified, the inside of the bubbles is decompressed and the inside pressure of the bubbles reaches 1 mmHg or less, and the thermal conductivity is also lowered to obtain an excellent heat insulating foam. Obtainable.

[0039]

[Table 2]

[0040]

As described above, according to the present invention, a heat insulating foam having good foam physical properties and excellent heat insulating properties can be obtained by using an alternative CFC foaming agent. Further, by using metallocene as the foaming nucleating agent, it is possible to obtain a heat-insulating foam having a performance that makes full use of the heat insulating property of the used foaming agent due to the gas. Further, according to the present invention, the gas or carbon dioxide of cyclopentadiene generated by foaming,
Since the inside of each of the bubbles is solidified, the inside of the bubbles is depressurized and can be evacuated to obtain excellent heat insulating performance. Furthermore, since it is possible to form a vacuum heat insulating body without a conventional depressurization vacuuming process, it is not always necessary to use a continuous cell urethane foam as the core material as in the conventional case, and a foamed resin composition having closed cell and high heat insulating property can be obtained. It can be a vacuum insulator. Further, since the foaming is directly carried out in a container having an arbitrary shape, a vacuum heat insulating body having an arbitrary shape can be formed in substantially the same manner as in-situ foaming of conventional urethane.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing a configuration example of a main part of a refrigerator box to which a heat insulating foam of the present invention is applied.

FIG. 2 is a schematic view showing a cross section of a heat insulating foam according to an embodiment of the present invention.

FIG. 3 is a schematic view showing a cross section of a heat insulating foam according to another embodiment of the present invention.

[Explanation of symbols]

 1 Outer Box 2 Inner Box 3 Urethane Foam Resin Composition 4 Metallocene 5 Bubbles 6 Container 7 Metallocene 8 Bubbles

Front page continuation (72) Inventor Takashi Hashida 1006 Kadoma, Kadoma-shi, Osaka, Matsushita Electric Industrial Co., Ltd. (72) Yoshio Kishimoto, 1006 Kadoma, Kadoma, Osaka Matsushita Electric Industrial

Claims (9)

[Claims] 1. A heat-insulating foam comprising a urethane foam resin composition and containing metallocene. 2. The heat insulating foam according to claim 1, wherein the urethane foamed resin composition contains metallocene having cyclopentadiene as a foaming agent immobilized therein, in the cells. 3. The heat insulating foam according to claim 2, wherein a compound in which carbon dioxide is immobilized is contained in the bubbles. 4. The metallocene is ferrocene.
The heat insulating foam according to any one of to 3. 5. A heat insulating foam comprising a urethane foam resin composition is formed by mixing and foaming a polyol composition, an isocyanate composition, and a foaming agent in which a metallocene as a foam nucleating agent is dispersed or dissolved. A method for producing a heat insulating foam, comprising: 6. A polyol composition, an isocyanate composition, a cyclopentadiene as a blowing agent, and a metallocene-reactive metal-containing composition which reacts with cyclopentadiene to form a metallocene are mixed and foamed. In the bubbles of the urethane foamed resin composition to be produced, cyclopentadiene is solidified as a metallocene by the reaction of the cyclopentadiene and the metallocene-reactive metal-containing composition, and the step of reducing the pressure in the bubbles is included. A method for producing a heat insulating foam. 7. A polyol composition, an isocyanate composition, a blowing agent cyclopentadiene and water, a metallocene-reactive metal-containing composition that reacts with cyclopentadiene to form a metallocene, and carbon dioxide are solidified. By mixing and foaming the solidification aid to, in the bubbles of the urethane foam resin composition to be produced, cyclopentadiene is solidified as a metallocene by the reaction between the cyclopentadiene and the metallocene-reactive metal-containing composition, A method for producing an adiabatic foam, comprising the step of solidifying carbon dioxide generated by a urea binding reaction between the water and the isocyanate composition with the solidification aid to reduce the pressure inside the bubbles. 8. The method for producing a heat insulating foam according to claim 6, wherein the metallocene-reactive metal-containing composition is composed of a metal halide and a basic compound. 9. The metallocene compound is ferrocene,
The method for producing a heat insulating foam according to claim 6 or 7, wherein the metallocene-reactive metal-containing composition comprises an iron dichloride compound and an amine compound or a metal hydroxide.