JP3362298B2 - Insulated box - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat insulating box body such as a refrigerator, a freezer and a showcase which uses a foamed heat insulating material such as hard urethane foam.

[0002]

2. Description of the Related Art Generally, in a heat insulating box such as a refrigerator, a raw material for a foamed heat insulating material such as hard urethane foam is injected into a space formed between an inner box and an outer box to form an integral foam. It is formed by this. CFC11 (trichlorofluoromethane), which is a foaming agent for foamed insulation, contains chlorine and has a slow decomposition rate, so its use is restricted worldwide as a cause of ozone layer depletion, and it is subject to CFC regulations. Therefore, we have to make an international reduction effort. Therefore, HCF is used as an alternative new blowing agent.
C141b (1.1-dichloro-1-fluoroethane)
Or, it has been unavoidable to apply a foamed heat insulating material using cyclopentane.

The properties required for the inner box of the heat-insulating box are a balance of physical properties of high rigidity and impact resistance, easy molding processability, excellent gloss appearance, HCFC141b (1) which is a foaming agent of hard urethane foam. -It may have stress crack resistance to 1-dichloro-1-fluoroethane) or cyclopentane. Further, since the extruded sheet is manufactured by vacuum forming, it is required that the sheet be easily extruded and have high mold reproducibility in vacuum forming.

On the other hand, a heat insulating material such as a rigid urethane foam is required to have not only heat insulating performance but also excellent filling property.

A heat insulating box integrally foamed with a heat insulating material containing HCFC141b or cyclopentane as a foaming agent will be described below.

The heat insulating box is composed of a heat insulating material containing HCFC141b or a heat insulating material containing cyclopentane integrally foamed in a space formed by connecting an inner box and an outer box.

In Japanese Patent Laid-Open No. 5-71013, the inner box is made of ABS resin or high-impact polystyrene resin laminated with acrylonitrile resin on the urethane foam contact surface. ing.

The behavior of the blowing agent HCFC141b or cyclopentane will be described below.
Or HC in the bubbles of insulation containing cyclopentane
Since FC141b has a boiling point of 32 ° C. and cyclopentane has a boiling point of 49 ° C., in a normal refrigerator use state, it exists in a gas state outside the refrigerator, in a liquid state inside the refrigerator, and in an intermediate region in a gas state. Although it exists as a liquid in two phases, it has a property that it is very easy to dissolve the resin in any state. That is, the molecule of HCFC141b or the molecule of cyclopentane swells into the resin in the inner box and cuts the molecular chain of the resin, so that minute crazes are generated. In this state, due to the temperature difference between the inside and outside of the refrigerator, the heat insulation box may warp in a pie-metal shape, causing a slight (1%
When a strain occurs (about below), the above-mentioned minute crazes expand, and finally, countless cracks of about 1 mm or more occur.

By constructing the urethane foam contact surface of the inner box with acrylonitrile resin, HCFC141b
Alternatively, it becomes almost insoluble in cyclopentane and the above-mentioned craze or crack does not occur.

[0010]

However, in the heat-insulating box body thus constructed, the resin forming the inner box is an unsaturated nitrile which undergoes depolymerization due to heat and is markedly colored. There was a problem that the inner box was discolored from yellow to brown due to heat during molding or vacuum forming, and the commercial value was lowered.

Further, since the acrylonitrile resin and the ABS resin or the high-impact polystyrene resin are completely incompatible with each other, the laminated sheet cannot be recycled.

In view of the above problems, the present invention does not discolor the inner box due to heat during sheet extrusion or vacuum forming, and the sheet or vacuum formed product can be recycled.
Moreover, it is an object of the present invention to provide a heat-insulating box that does not cause crazes or cracks even with the strong chemical attack of HCFC141b or cyclopentane.

[0013]

[Means for Solving the Problems] In order to solve this problem,
The heat insulating box body of the present invention comprises a urethane heat insulating material integrally foamed between both a resin inner box and a metal outer box, wherein the urethane heat insulating material is a polyol, a foam stabilizer, a catalyst,
HCFC141b or cyclopentane as a foaming agent,
Polymeric MDI or its prepolymer compound is 40 to 100% by weight as an isocyanate component, and the remainder is TDI-80, crude TDI and an organic polyisocyanate having its prepolymerized product, and the resin inner box serves as an adhesive layer. It has a three-layer structure of a surface layer and an intermediate layer, and the adhesive layer that adheres to the urethane heat insulating material is 50 to 50
A copolymer obtained by polymerizing a monomer mixture of 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound is used, the surface layer of which is aromatic vinyl in the presence of a conjugated diene-based synthetic rubber. A graft obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber as an intermediate layer, which is a mixture of a graft copolymer obtained by polymerizing a compound monomer and an aromatic vinyl polymer. A resin composition is obtained by mixing a mixture of a copolymer and an aromatic vinyl polymer and a crushed product of a resin inner box material comprising the adhesive layer, the surface layer and the intermediate layer.

According to this invention, the blowing agent HCFC1
The adhesive prevents 41b or cyclopentane from penetrating into the resin, and the inner box resin does not craze or crack. Also,
Depending on the composition of the surface layer, there is no discoloration during sheet extrusion or vacuum forming because it has gloss and high thermal stability. Further, as the intermediate layer, a crushed product of another discarded inner box including an adhesive layer, an intermediate layer and a surface layer is used as a recycling material. Therefore, the inner box can be used by recycling the material.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention is a heat insulating box body made of urethane heat insulating material integrally foamed between a resin inner box and a metal outer box. Urethane insulation is polyol, foam stabilizer, catalyst, H as foaming agent
CFC141b or cyclopentane, 40 to 100% by weight of polymeric MDI or its prepolymerized compound as an isocyanate component, and the remainder is TDI-80,
It has a crude TDI and an organic polyisocyanate as a prepolymerized product thereof, and the resin inner box has a three-layer structure of an adhesive layer, a surface layer, and an intermediate layer, and the adhesive layer for bonding the urethane heat insulating material is 50 To 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a monomer mixture of a methyl methacrylate compound to obtain a copolymer, the surface layer of which is aromatic in the presence of a conjugated diene-based synthetic rubber. A mixture of a graft copolymer obtained by polymerizing a vinyl compound monomer and an aromatic vinyl polymer, and an intermediate layer was obtained by polymerizing the aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. A resin composition is obtained by mixing a mixture of a graft copolymer and an aromatic vinyl polymer and a crushed product of a resin inner box material comprising the adhesive layer, the surface layer and the intermediate layer.

With the above structure, a monomer mixture of 50 to 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound, which constitutes an adhesive layer with the urethane heat insulating material of the inner box, is polymerized. The copolymer thus obtained prevents the permeation of the blowing agent into the inside of the resin by HCFC141b or cyclopentane. Therefore, the strong chemical attack of HCFC141b or cyclopentane does not cause the molecular chain of the resin to be cleaved. It has the effect of preventing cracking. Further, the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer is glossy and has high thermal stability. There is an effect that the appearance performance is improved without being discolored by heat during extrusion or vacuum forming. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber There is an effect that it can be recycled as. The urethane heat insulating material has excellent fluidity and can uniformly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

The invention according to claim 2 of the present invention is
The surface layer according to claim 1 is a copolymer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer, and constitutes an adhesive layer with the urethane heat insulating material of the inner box. 50 to 95% by weight of an aromatic vinyl compound and 5 to
A copolymer obtained by polymerizing a monomer mixture of 50% by weight of a methyl methacrylate compound is HCFC141 as a foaming agent.
Since b or cyclopentane is prevented from penetrating into the inside of the resin, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being cleaved, so that crazes and cracks can be prevented. In addition, the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability and therefore discolors by heat during sheet extrusion or vacuum forming. There is an effect that the external appearance performance is improved without any occurrence. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Including the three-layer structure, the mixture was pulverized and mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer, and an intermediate layer. There is an effect that it can be recycled as. The urethane heat insulating material has excellent fluidity and can uniformly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

The invention according to claim 3 of the present invention is
The surface layer according to claim 1 is a polymer alloy of polypropylene and a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. 50 to 95% by weight, which constitutes the adhesive layer with the urethane heat insulating material of the inner box
The copolymer obtained by polymerizing a monomer mixture of the aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound prevents HCFC141b of the blowing agent or cyclopentane from penetrating into the resin. Cyclopentane has a strong chemical attack property, and since the molecular chain of the resin is not cut, it is effective in preventing crazes and cracks. Further, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber of the surface layer, and a polymer alloy of polypropylene have impact resistance. It is high, and even if there is a notch, the propagation of cracks is small, so damage to the sheet or vacuum formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, there is an effect that the appearance performance is improved without being discolored by heat during sheet extrusion or vacuum forming. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Including the three-layer structure, the mixture was pulverized and mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer, and an intermediate layer. There is an effect that it can be recycled as. The urethane heat insulating material has excellent fluidity and can uniformly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

The invention described in claim 4 is the same as that of claim 1.
Graft copolymer obtained by polymerizing the surface layer in the description with a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. Combined with vinyl cyanide compound 5
It is a mixture of 25% by weight and a copolymer of 75 to 95% by weight of an aromatic vinyl compound, and 50 to 95% by weight of an aromatic vinyl compound constituting an adhesive layer with the urethane heat insulating material of the inner box. A copolymer obtained by polymerizing a monomer mixture of 5 to 50% by weight of a methyl methacrylate compound prevents permeation of HCFC141b or cyclopentane, which is a foaming agent, into the resin, so that HCFC141b or cyclopentane has a strong chemical attack. As a result, the molecular chain of the resin is not cut, so that there is an effect that crazes and cracks can be prevented. Further, a graft copolymer obtained by polymerizing a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber in the surface layer. Combined, vinyl cyanide compound 5 to 25 wt% and aromatic vinyl compound 75 to 9
The mixture of 5% by weight of the copolymer has high chemical resistance and does not easily generate cracks even when it comes into contact with edible oil. Also, it has gloss and high thermal stability, so that it can be exposed to heat during sheet extrusion or vacuum forming. It has the effect of improving the appearance performance without discoloration. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber There is an effect that it can be recycled as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

The invention described in claim 5 is the same as claim 1.
A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber to form an adhesive layer that adheres to the urethane heat insulating material in the description, and a polypropylene polymer. Due to the alloy, the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box and the aromatic vinyl polymer Since the mixture of the coalesce and the polymer alloy of polypropylene prevent the penetration of the blowing agent into the inside of the resin of HCFC141b or cyclopentane, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being cut. It can prevent crazes and cracks. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, the sheet or the vacuum-formed product is less likely to be damaged. In addition, since the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer is glossy and has high thermal stability, the sheet The appearance performance is improved without discoloration due to heat during extrusion or vacuum forming. Also,
Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, three layers including the intermediate layer are included. Layer structure is pulverized and mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber, and recycled as an intermediate layer Can be used. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

The invention according to claim 6 is the same as claim 2
A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber to form an adhesive layer that adheres to the urethane heat insulating material in the description, and a polypropylene polymer. Alloy, a graft copolymer and aromatic vinyl obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box The mixture of polymers and the polymer alloy of polypropylene prevent the permeation of the blowing agent into the inside of the resin of HCFC141b or cyclopentane. Therefore, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being cut. Therefore, crazes and cracks can be prevented. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, the sheet or the vacuum-formed product is less likely to be damaged. In addition, since the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability, it is discolored by heat during sheet extrusion or vacuum forming. And the appearance performance is improved. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

The invention described in claim 7 is the same as claim 3
A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber to form an adhesive layer that adheres to the urethane heat insulating material in the description, and a polypropylene polymer. Alloy, a graft copolymer and aromatic vinyl obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box The mixture of polymers and the polymer alloy of polypropylene prevent the permeation of the blowing agent into the inside of the resin of HCFC141b or cyclopentane. Therefore, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being cut. Therefore, crazes and cracks can be prevented. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, the sheet or the vacuum-formed product is less likely to be damaged. Further, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber of the surface layer, and a polymer alloy of polypropylene have impact resistance. It is high, and even if there is a notch, the propagation of cracks is small, so damage to the sheet or vacuum formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, it does not discolor due to heat during sheet extrusion or vacuum forming, and the appearance performance is improved. Further, the adhesive layer and the surface layer with the urethane heat insulating material have a high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, and thus the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and the graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber There is an effect that it can be recycled as. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The invention described in claim 8 is the invention according to claim 7.
Graft copolymer obtained by polymerizing the surface layer in the description with a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. Combined with vinyl cyanide compound 5
Aromatic vinyl in the presence of a conjugated diene-based synthetic rubber forming an adhesive layer with the urethane heat insulating material of the inner box, which is a mixture of a copolymer of 25% by weight and an aromatic vinyl compound of 75 to 95% by weight. A mixture of a graft copolymer obtained by polymerizing a compound monomer and an aromatic vinyl polymer, and a polymer alloy of polypropylene prevent penetration of HCFC141b or cyclopentane, which is a blowing agent, into the resin.
Due to the strong chemical attack of CFC141b or cyclopentane, the molecular chain of the resin is not cut, so crazes and cracks can be prevented. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, the sheet or the vacuum-formed product is less likely to be damaged. Further, a graft copolymer obtained by polymerizing a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber in the surface layer. The mixture and the mixture of the vinyl cyanide compound 5 to 25% by weight and the aromatic vinyl compound 75 to 95% by weight have a high chemical resistance and are less likely to crack even when they come into contact with edible oil. Since it is glossy and has high thermal stability, it does not discolor due to heat during sheet extrusion or vacuum forming, resulting in higher appearance performance. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Including the three-layer structure crushed,
It can be recycled and used as an intermediate layer by mixing it with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

The invention according to claim 9 is the same as that of claim 8.
Graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber as an adhesive layer for adhering to the urethane heat insulating material described in the above, surface layer Is a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer, and is adhered to the urethane heat insulating material in the inner box. A graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber constituting a layer is a foaming agent HCFC141b or cyclopentane. HC is absorbed and prevents penetration into the resin.
Due to the strong chemical attack of FC141b or cyclopentane, the molecular chain of the resin is not cut and crazes and cracks can be prevented. In addition, since the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer is glossy and has high thermal stability, the sheet The appearance performance is improved without discoloration due to heat during extrusion or vacuum forming. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

Further, the invention according to claim 10 is a copolymer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer for the surface layer according to claim 9. , A graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber forming an adhesive layer with a urethane heat insulating material of an inner box However, since it absorbs HCFC141b or cyclopentane as a foaming agent and prevents it from penetrating into the inside of the resin, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being cut and prevents crazes and cracks. In addition, since the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability, it is discolored by heat during sheet extrusion or vacuum forming. And the appearance performance is improved. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

The invention according to claim 11 is a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the surface layer according to claim 10 in the presence of a conjugated diene-based synthetic rubber, and an aromatic compound. A mixture of a group vinyl polymer and a polymer alloy of polypropylene, which is an aromatic vinyl compound alone in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber forming an adhesive layer with a urethane heat insulating material of an inner box. The graft copolymer obtained by polymerizing 70 to 90% by weight of the monomer absorbs HCFC141b or cyclopentane as the foaming agent and prevents the penetration into the resin.
Or with the strong chemical attack of cyclopentane,
The molecular chain of the resin is not cut, and crazes and cracks can be prevented. Further, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber of the surface layer, and a polymer alloy of polypropylene have impact resistance. It is high, and even if there is a notch, the propagation of cracks is small, so damage to the sheet or vacuum formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, it does not discolor due to heat during sheet extrusion or vacuum forming, and the appearance performance is improved. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

According to a twelfth aspect of the present invention, the surface layer according to the eleventh aspect is used in the presence of a conjugated diene-based synthetic rubber in an amount of 5 to 25% by weight of a vinyl cyanide compound and 75 to 9%.
Graft copolymer obtained by polymerizing a monomer mixture with 5% by weight of an aromatic vinyl compound, 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound
10 is a mixture of the above copolymers and is a conjugated diene-based synthetic rubber that forms an adhesive layer with the urethane heat insulating material of the inner box.
Aromatic vinyl compound monomer 70 in the presence of
The graft copolymer obtained by polymerizing ~ 90 wt% absorbs the blowing agent HCFC141b or cyclopentane and prevents the permeation into the resin. It is not cut and can prevent crazes and cracks. Further, in the presence of the conjugated diene-based synthetic rubber of the surface layer, 5 to 25% by weight of the vinyl cyanide compound and 75 to 95% by weight are used.
Graft copolymer obtained by polymerizing a monomer mixture with a weight percent of an aromatic vinyl compound, and a vinyl cyanide compound 5
A mixture of a copolymer of 25 to 25 wt% and an aromatic vinyl compound of 75 to 95 wt% has high chemical resistance, is less likely to crack when contacted with edible oil, and is glossy and has high thermal stability. Therefore, the appearance performance is improved without being discolored by heat during sheet extrusion or vacuum forming. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

According to a thirteenth aspect of the present invention, the adhesive layer for adhering to the urethane heat insulating material according to the twelfth aspect is used in the presence of a conjugated diene-based synthetic rubber in an amount of 5 to 25% by weight of a vinyl cyanide compound and 75 to 50% by weight. A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture is a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer as a mixture, and a urethane in an inner box. 5 to 25% by weight of a vinyl cyanide compound in the presence of a conjugated diene-based synthetic rubber forming an adhesive layer with a heat insulating material and 75
Graft copolymer obtained by polymerizing a monomer mixture with ˜95 wt% aromatic vinyl compound, copolymer with 5 to 25 wt% vinyl cyanide compound and 75 to 95 wt% aromatic vinyl compound The mixture of has high chemical resistance and is a blowing agent of HC.
Since FC141b or cyclopentane is prevented from penetrating into the resin, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being broken, and prevents crazes and cracks. In addition, since the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer is glossy and has high thermal stability, the sheet The appearance performance is improved without discoloration due to heat during extrusion or vacuum forming. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

Further, the invention according to claim 14 is that the surface layer according to claim 13 is a copolymer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer. , A monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber forming an adhesive layer with the urethane heat insulating material of the inner box The mixture of the graft copolymer obtained by polymerizing the vinyl cyanide compound and the copolymer of 5 to 25% by weight of the vinyl cyanide compound and 75 to 95% by weight of the aromatic vinyl compound has high chemical resistance, and HCFC141b or a cyclohexene blowing agent. HCFC14 is used to prevent the penetration of pentane into the resin.
Due to the strong chemical attack of 1b or cyclopentane, the molecular chain of the resin is not cut and crazes and cracks can be prevented. In addition, since the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability, it is discolored by heat during sheet extrusion or vacuum forming. And the appearance performance is improved. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Including the three-layer structure crushed,
It can be recycled and used as an intermediate layer by mixing it with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

According to a fifteenth aspect of the present invention, the adhesive layer for adhering to the urethane heat insulating material according to the fourteenth aspect comprises 5 to 25% by weight of a vinyl cyanide compound and 75 to 50% by weight in the presence of a conjugated diene synthetic rubber. A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. As a mixture, the surface layer is a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber, and a polymer alloy of polypropylene. Yes, in the presence of the conjugated diene-based synthetic rubber that forms the adhesive layer with the urethane heat insulating material of the inner box, 5 to 25
Graft copolymer obtained by polymerizing a monomer mixture of vinyl cyanide compound of 75% by weight and aromatic vinyl compound of 75 to 95% by weight, vinyl cyanide compound of 5 to 25% by weight and aromatic vinyl compound The mixture of 75 to 95% by weight of the copolymer has high chemical resistance and prevents the penetration of HCFC141b or cyclopentane of the foaming agent into the resin.
Due to the strong chemical attack of FC141b or cyclopentane, the molecular chain of the resin is not cut and crazes and cracks can be prevented. Further, a graft copolymer aromatic vinyl polymer mixture obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber of the surface layer, and a polymer alloy of polypropylene have high impact resistance. Even if there is a notch, the propagation of cracks is small, so that damage to the sheet or the vacuum-formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, it does not discolor due to heat during sheet extrusion or vacuum forming, and the appearance performance is improved. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

According to a sixteenth aspect of the present invention, the surface layer according to the fifteenth aspect comprises the vinyl cyanide compound in an amount of 5 to 25% by weight and 75 to 9% by weight in the presence of the conjugated diene-based synthetic rubber.
Graft copolymer obtained by polymerizing a monomer mixture with 5% by weight of an aromatic vinyl compound, 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound
In the presence of a conjugated diene-based synthetic rubber that forms an adhesive layer with the urethane heat insulating material of the inner box, in the presence of 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and HCF as a foaming agent.
Since C141b or cyclopentane is prevented from penetrating into the resin, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being broken and prevents crazes and cracks. Further, a graft copolymer obtained by polymerizing a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber in the surface layer. The mixture and the mixture of the vinyl cyanide compound 5 to 25% by weight and the aromatic vinyl compound 75 to 95% by weight have a high chemical resistance and are less likely to crack even when they come into contact with edible oil. Since it is glossy and has high thermal stability, it does not discolor due to heat during sheet extrusion or vacuum forming, resulting in higher appearance performance. Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, the intermediate layer is formed. Intermediate layer mixed with a mixture of aromatic vinyl polymer and graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the presence of conjugated diene-based synthetic rubber Can be recycled and used as. The urethane heat insulating material has excellent fluidity, can uniformly fill the space between the inner box and the outer box, and can provide a heat insulating box having high heat insulating performance.

The heat insulating box of the present invention will be described below with reference to specific embodiments. (Embodiment 1) Claim 1 of the present invention will be described. A copolymer obtained by polymerizing an adhesive layer with a urethane heat insulating material with a monomer mixture of 50 to 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound, and a conjugated diene-based surface layer. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a synthetic rubber, and an intermediate layer in the presence of a conjugated diene-based synthetic rubber. A mixture of a graft copolymer obtained by polymerizing a polymer and an aromatic vinyl polymer, and the adhesive layer,
A three-layer structure sheet made of a resin composition in which a crushed product of a resin inner box material composed of a surface layer and an intermediate layer was mixed was coextrusion-molded.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two kinds of urethane heat insulating materials are used, and an aromatic amine-based polyether (OH value: 440 mg) is used as a polyol.
KOH / g) 100 parts by weight, Shin-Etsu Chemical Co., Ltd. F-338 1.5 parts by weight as a foam stabilizer, and Kao Co., Ltd. Kalyzer No. as a catalyst. 1 is 2 parts by weight, HCFC141b is 38 parts by weight as a foaming agent, and prepolymer TDI (amine equivalent 150) 50 is an isocyanate component.
HCFC 141b consisting of 14 parts by weight of a mixture of 50% by weight of crude TDI (amine equivalent 120) and 105 parts of a mixture of 50% by weight of polymeric MDI (amine equivalent 135) and 50% of prepolymer MDI (amine equivalent 150). One type of heat insulating material containing was used.

Another type is an aromatic amine type polyether (OH value 440 mgKOH / g) 1 as a polyol.
00 parts by weight, F-338 manufactured by Shin-Etsu Chemical Co., Ltd. as a foam stabilizer
1.5 parts by weight of Kaolizer No. manufactured by Kao Corporation as a catalyst. 2 parts by weight of 1 and 1 of cyclopentane as a foaming agent
5 parts by weight and prepolymer T as an isocyanate component
DI (amine equivalent 150) 50% by weight and crude TDI
Thermal insulation containing cyclopentane consisting of 14 parts by weight of a mixture of 50% by weight (amine equivalent 120), 105 parts by weight of a mixture of 50% by weight of polymeric MDI (amine equivalent 135) and 50% by weight of prepolymer MDI (amine equivalent 150). One type was used.

The heat-insulating box body of the present invention thus produced has a good reproducibility of the mold at the time of vacuum forming as the inner box quality, and 50 to 9 constituting the adhesive layer with the urethane heat insulating material of the inner box.
A copolymer obtained by polymerizing a monomer mixture of 5% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound prevents permeation of HCFC141b of a blowing agent or cyclopentane into a resin. So HCFC141
b or cyclopentane has a strong chemical attack property, the molecular chain of the resin is not broken, and 60 ° C /-
Crazes and cracks did not occur even when thermal shock was given by performing 5 cycles of the 25 ° C. thermal cycle test.

Further, the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer is glossy and has thermal stability. Since it is expensive, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can uniformly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

(Embodiment 2) Next, claim 2 of the present invention will be described. 50-95 adhesive layer with urethane insulation
Copolymer obtained by polymerizing a monomer mixture of 5% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound, a surface layer having a conjugated diene compound monomer and an aromatic vinyl compound monomer The copolymer obtained by polymerizing the intermediate layer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for the intermediate layer, and A three-layer structure sheet made of a resin composition in which a crushed resin inner box material consisting of an adhesive layer, a surface layer and an intermediate layer was mixed was coextrusion-molded.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility at the time of vacuum forming as the inner-box quality, and 50 to 95% by weight of the fragrance constituting the adhesive layer with the urethane heat-insulating material of the inner box. The copolymer obtained by polymerizing a monomer mixture of a vinyl group vinyl compound and 5 to 50% by weight of a methyl methacrylate compound prevents permeation of HCFC141b or cyclopentane, which is a foaming agent, into the resin.
Due to the strong chemical attack of C141b or cyclopentane, the molecular chain of the resin will not be broken.
Even when a thermal shock test was conducted by carrying out 5 cycles of the cooling / heating cycle test at .degree. C./-25.degree.

Further, the copolymer obtained by polymerizing the conjugated diene compound monomer and the aromatic vinyl compound monomer in the surface layer is glossy and has high thermal stability. The appearance performance could be maintained high without discoloration.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can uniformly fill the space between the inner box and the outer box, so that a heat insulating box having high heat insulating performance can be obtained.

(Third Embodiment) The third aspect of the present invention will be described. 50-95 adhesive layer with urethane insulation
A copolymer obtained by polymerizing a monomer mixture of 5% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound, the surface layer of which is an aromatic vinyl compound alone in the presence of a conjugated diene synthetic rubber. A mixture of a graft copolymer obtained by polymerizing a monomer and an aromatic vinyl polymer, a polymer alloy of polypropylene, and an intermediate layer by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. A three-layer sheet having a resin composition obtained by mixing the obtained mixture of the graft copolymer and the aromatic vinyl polymer and the crushed product of the resin inner box material including the adhesive layer, the surface layer and the intermediate layer is used. It was prepared by extrusion molding.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility at the time of vacuum forming as the inner-box quality, and 50 to 95% by weight of the fragrance constituting the adhesive layer with the urethane heat-insulating material of the inner box. The copolymer obtained by polymerizing a monomer mixture of a vinyl group vinyl compound and 5 to 50% by weight of a methyl methacrylate compound prevents permeation of HCFC141b or cyclopentane, which is a foaming agent, into the resin.
Due to the strong chemical attack of C141b or cyclopentane, the molecular chain of the resin will not be broken.
Even when a thermal shock test was conducted by carrying out 5 cycles of the cooling / heating cycle test at .degree. C./-25.degree.

Further, a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber of the surface layer and an aromatic vinyl polymer, and a polymer alloy of polypropylene are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, and the damage to the sheet or vacuum-formed product is unlikely to occur. In addition, since it is glossy and has high thermal stability, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has excellent fluidity and can uniformly fill the space between the inner box and the outer box, and a heat insulating box having high heat insulating performance can be obtained.

(Fourth Embodiment) The fourth aspect of the present invention will be described. 50-95 adhesive layer with urethane insulation
A copolymer obtained by polymerizing a monomer mixture of 5% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound, the surface layer of which is 5 to 5% in the presence of a conjugated diene-based synthetic rubber.
25% by weight vinyl cyanide compound and 75-95% by weight
Graft copolymer obtained by polymerizing a monomer mixture with the aromatic vinyl compound, and a vinyl cyanide compound 5 to 25
Graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in a mixture of a copolymer of 50% by weight and an aromatic vinyl compound of 75 to 95% by weight, and an aromatic A three-layer structure sheet made of a resin composition was prepared by co-extruding a mixture of a group vinyl polymer and a crushed product of a resin inner box material comprising the adhesive layer, the surface layer and the intermediate layer.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two kinds of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility at the time of vacuum forming as the inner-box quality, and 50 to 95% by weight of the fragrance constituting the adhesive layer with the urethane heat-insulating material of the inner box. The copolymer obtained by polymerizing a monomer mixture of a vinyl group vinyl compound and 5 to 50% by weight of a methyl methacrylate compound prevents permeation of HCFC141b or cyclopentane, which is a foaming agent, into the resin.
Due to the strong chemical attack of C141b or cyclopentane, the molecular chain of the resin will not be broken.
Even when a thermal shock test was conducted by carrying out 5 cycles of the cooling / heating cycle test at .degree. C./-25.degree.

In the presence of the conjugated diene-based synthetic rubber for the surface layer, 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack even when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and has excellent appearance performance. I could keep it high.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box having a high heat insulating performance can be obtained.

(Fifth Embodiment) The fifth aspect of the present invention will be described. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for an adhesive layer with a urethane heat insulating material, a polymer alloy of polypropylene, and a surface A layer is a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber, and an intermediate layer is aromatic in the presence of a conjugated diene-based synthetic rubber. A resin obtained by mixing a mixture of a graft copolymer obtained by polymerizing a vinyl group monomer and an aromatic vinyl polymer, and a crushed product of a resin inner box material including the adhesive layer, the surface layer and the intermediate layer. A sheet having a three-layer structure as the composition was co-extruded and formed.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. A graft copolymer obtained by polymerizing an aromatic vinyl compound monomer below, a mixture of an aromatic vinyl polymer, and a polymer alloy of polypropylene permeate the blowing agent HCFC141b or cyclopentane into the resin. Since it prevents HCFC141b or cyclopentane from having a strong chemical attack, the molecular chain of the resin is not broken, and even if it is subjected to 5 cycles of 60 ° C / -25 ° C thermal cycling test, it is subject to crazes and cracks. Did not occur.

Further, the mixture of the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer and the aromatic vinyl polymer is glossy and has thermal stability. Since it is expensive, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazing or cracking occurred and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box having high heat insulating performance can be obtained.

(Sixth Embodiment) The sixth aspect of the present invention will be described. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for an adhesive layer with a urethane heat insulating material, a polypropylene polymer alloy, and a surface. Copolymer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer for the layer, and an intermediate layer by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber A sheet having a three-layer structure made of a resin composition obtained by mixing a mixture of the graft copolymer and the aromatic vinyl polymer and a crushed product of the resin inner box material including the adhesive layer, the surface layer, and the intermediate layer. It was prepared by extrusion molding.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two kinds of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus prepared has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer below and an aromatic vinyl polymer, and a polymer alloy of polypropylene prevent permeation of HCFC141b or cyclopentane as a foaming agent into the resin. Therefore, due to the strong chemical attack of HCFC141b or cyclopentane, the molecular chain of the resin is not broken, and even when subjected to thermal shock tests at 60 ° C / -25 ° C for 5 cycles, crazes and cracks are generated. Did not occur.

Further, since the copolymer obtained by polymerizing the conjugated diene compound monomer and the aromatic vinyl compound monomer in the surface layer is glossy and has high thermal stability, it is possible to improve the heat during sheet extrusion or vacuum forming. The appearance performance could be maintained high without discoloration.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

(Embodiment 7) A seventh aspect of the present invention will be described. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for an adhesive layer with a urethane heat insulating material, a polypropylene polymer alloy, and a surface. A layer of a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber, a polymer alloy of polypropylene, and a conjugated diene-based synthesis of the intermediate layer. A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of rubber and an aromatic vinyl polymer, and a resin inner box material comprising the adhesive layer, the surface layer and the intermediate layer. A sheet having a three-layer structure as a resin composition in which crushed products were mixed was coextrusion-molded to prepare.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus prepared has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer below and an aromatic vinyl polymer, and a polymer alloy of polypropylene prevent permeation of HCFC141b or cyclopentane as a foaming agent into the resin. Therefore, due to the strong chemical attack of HCFC141b or cyclopentane, the molecular chain of the resin is not broken, and even when subjected to thermal shock tests at 60 ° C / -25 ° C for 5 cycles, crazes and cracks are generated. Did not occur.

A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for the surface layer and an aromatic vinyl polymer, and a polymer alloy of polypropylene are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, so it is less likely that the sheet or vacuum-formed product will be damaged. In addition, since it is glossy and has high thermal stability, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box having high heat insulating performance can be obtained.

(Embodiment 8) Further, claim 8 of the present invention will be described. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for an adhesive layer with a urethane heat insulating material, a polypropylene polymer alloy, and a surface. A graft copolymer obtained by polymerizing a layer with a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber; A mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and an intermediate layer are obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. A sheet having a three-layer structure made of a resin composition obtained by mixing a mixture of the graft copolymer and the aromatic vinyl polymer and a crushed product of the resin inner box material including the adhesive layer, the surface layer, and the intermediate layer. Extruded It was created.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two kinds of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus prepared has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer below and an aromatic vinyl polymer, and a polymer alloy of polypropylene prevent permeation of HCFC141b or cyclopentane as a foaming agent into the resin. Therefore, due to the strong chemical attack of HCFC141b or cyclopentane, the molecular chain of the resin is not broken, and even when subjected to thermal shock tests at 60 ° C / -25 ° C for 5 cycles, crazes and cracks are generated. Did not occur.

In the presence of the conjugated diene-based synthetic rubber for the surface layer, 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack even when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and has excellent appearance performance. I could keep it high.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, and a heat insulating box having high heat insulating performance can be obtained.

(Ninth Embodiment) The ninth aspect of the present invention will be described. Graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene synthetic rubber as an adhesive layer with a urethane heat insulating material, and a conjugated diene as a surface layer. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of an aromatic vinyl compound monomer, and an intermediate layer in the presence of a conjugated diene synthetic rubber. A resin composition was obtained by mixing a mixture of a graft copolymer obtained by polymerizing a monomer and an aromatic vinyl polymer, and a crushed product of a resin inner box material composed of the adhesive layer, the surface layer and the intermediate layer. A sheet having a three-layer structure was coextruded and formed.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between the two boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility at the time of vacuum forming as the inner box quality, and the conjugated diene-based synthetic rubber 10 to 10 that constitutes the adhesive layer with the urethane heat insulating material of the inner box. A graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 30% by weight absorbs HCFC141b or cyclopentane as a foaming agent and permeates the foaming agent into the resin. Because it prevents HCFC141b or cyclopentane's strong chemical attack, the molecular chain of the resin is not broken, and 60 ℃ / -25 ℃ thermal cycle test is performed.
Even when subjected to thermal shock by cycling, crazes and cracks did not occur.

Further, the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber of the surface layer is glossy and also has thermal stability. Since it is expensive, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

(Embodiment 10) Also, the present invention claimed in claim 1
0 will be described. Graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene synthetic rubber as an adhesive layer with a urethane heat insulating material, and a conjugated diene as a surface layer. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of an aromatic vinyl compound monomer, and an intermediate layer in the presence of a conjugated diene synthetic rubber. A resin composition was obtained by mixing a mixture of a graft copolymer obtained by polymerizing a monomer and an aromatic vinyl polymer, and a crushed product of a resin inner box material composed of the adhesive layer, the surface layer and the intermediate layer. A sheet having a three-layer structure was coextruded and formed.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two kinds of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility at the time of vacuum forming as the inner box quality, and the conjugated diene-based synthetic rubber 10 to 10 that constitutes the adhesive layer with the urethane heat insulating material of the inner box. A graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 30% by weight absorbs HCFC141b or cyclopentane as a foaming agent and permeates the foaming agent into the resin. Because it prevents HCFC141b or cyclopentane's strong chemical attack, the molecular chain of the resin is not broken, and 60 ℃ / -25 ℃ thermal cycle test is performed.
Even when subjected to thermal shock by cycling, crazes and cracks did not occur.

Further, the copolymer obtained by polymerizing the conjugated diene compound monomer and the aromatic vinyl compound monomer in the surface layer is glossy and has high thermal stability. The appearance performance could be maintained high without discoloration.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

(Embodiment 11) In addition, claim 1 of the present invention
1 will be described. Graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene synthetic rubber as an adhesive layer with a urethane heat insulating material, and a conjugated diene as a surface layer. In the presence of a conjugated diene-based synthetic rubber, a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer and an aromatic vinyl polymer in the presence of a system-based synthetic rubber, a polypropylene polymer alloy, and an intermediate layer A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer with an aromatic vinyl polymer and a crushed resin inner box material consisting of the adhesive layer, surface layer and intermediate layer are mixed. A sheet having a three-layer structure as the resin composition was prepared by coextrusion molding.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two kinds of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility at the time of vacuum forming as the inner box quality, and the conjugated diene-based synthetic rubber 10 to 10 that constitutes the adhesive layer with the urethane heat insulating material of the inner box. A graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 30% by weight absorbs HCFC141b or cyclopentane as a foaming agent and permeates the foaming agent into the resin. Because it prevents HCFC141b or cyclopentane's strong chemical attack, the molecular chain of the resin is not broken, and 60 ℃ / -25 ℃ thermal cycle test is performed.
Even when subjected to thermal shock by cycling, crazes and cracks did not occur.

A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in the surface layer and an aromatic vinyl polymer, and a polymer alloy of polypropylene are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, and the damage to the sheet or vacuum-formed product is unlikely to occur. In addition, since it is glossy and has high thermal stability, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

(Embodiment 12) Also, the present invention claimed in claim 1
2 will be explained. Graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene synthetic rubber as an adhesive layer with a urethane heat insulating material, and a conjugated diene as a surface layer. 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight in the presence of a synthetic rubber.
Graft copolymer obtained by polymerizing a monomer mixture with a weight percent of an aromatic vinyl compound, and a vinyl cyanide compound 5
~ 25 wt% and aromatic vinyl compound 75-95 wt% copolymer, graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the middle layer in the presence of conjugated diene-based synthetic rubber Created by co-extrusion molding a three-layer structure sheet made of a resin composition in which a mixture of styrene and an aromatic vinyl polymer and a crushed product of a resin inner box material consisting of the adhesive layer, surface layer, and intermediate layer are mixed. did.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus produced has good mold reproducibility at the time of vacuum forming as the inner box quality, and the conjugated diene-based synthetic rubber 10 to 10 that constitutes the adhesive layer with the urethane heat insulating material of the inner box. A graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 30% by weight absorbs HCFC141b or cyclopentane as a foaming agent and permeates the foaming agent into the resin. Because it prevents HCFC141b or cyclopentane's strong chemical attack, the molecular chain of the resin is not broken, and 60 ℃ / -25 ℃ thermal cycle test is performed.
Even when subjected to thermal shock by cycling, crazes and cracks did not occur.

Further, in the presence of the conjugated diene-based synthetic rubber of the surface layer, 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack even when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and has excellent appearance performance. I could keep it high.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box having a high heat insulating performance can be obtained.

(Thirteenth Embodiment) The present invention also provides claim 1.
3 will be explained. An adhesive layer with a urethane heat insulating material was obtained by polymerizing a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. A graft copolymer,
A mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and a surface layer are obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. Of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber as a mixture of a graft copolymer and an aromatic vinyl polymer. A sheet having a three-layer structure, which is a resin composition obtained by mixing a mixture and a crushed product of a resin inner box material including the adhesive layer, the surface layer, and the intermediate layer, was co-extruded and formed.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus prepared has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. Graft copolymer obtained by polymerizing a monomer mixture of 5 to 25 wt% vinyl cyanide compound and 75 to 95 wt% aromatic vinyl compound below, and 5 to 25 wt% vinyl cyanide compound A mixture of a copolymer of 75 to 95% by weight of an aromatic vinyl compound has high chemical resistance and prevents HCFC141b of a foaming agent or cyclopentane from penetrating into the resin.
Or with the strong chemical attack of cyclopentane,
60 ° C / -25 without breaking the resin molecular chain
Even when subjected to a thermal shock test of 5 ° C. for 5 cycles, crazes and cracks did not occur.

The mixture of the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer and the aromatic vinyl polymer is glossy and also has thermal stability. Since it is expensive, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box having high heat insulating performance can be obtained.

(Embodiment 14) Further, the present invention is defined in claim 1.
4 will be explained. An adhesive layer with a urethane heat insulating material was obtained by polymerizing a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. A graft copolymer,
A mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and a surface layer are obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. Of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber as a mixture of a graft copolymer and an aromatic vinyl polymer. A sheet having a three-layer structure, which is a resin composition obtained by mixing a mixture and a crushed product of a resin inner box material including the adhesive layer, the surface layer, and the intermediate layer, was co-extruded and formed.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two kinds of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus prepared has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. Graft copolymer obtained by polymerizing a monomer mixture of 5 to 25 wt% vinyl cyanide compound and 75 to 95 wt% aromatic vinyl compound below, and 5 to 25 wt% vinyl cyanide compound A mixture of a copolymer of 75 to 95% by weight of an aromatic vinyl compound has high chemical resistance and prevents HCFC141b of a foaming agent or cyclopentane from penetrating into the resin.
Or with the strong chemical attack of cyclopentane,
60 ° C / -25 without breaking the resin molecular chain
Even when subjected to a thermal shock test of 5 ° C. for 5 cycles, crazes and cracks did not occur.

Further, the copolymer obtained by polymerizing the conjugated diene compound monomer and the aromatic vinyl compound monomer in the surface layer is glossy and has high thermal stability. The appearance performance could be maintained high without discoloration.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

(Fifteenth Embodiment) Further, the present invention is defined in claim 1.
5 will be explained. An adhesive layer with a urethane heat insulating material was obtained by polymerizing a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. A graft copolymer,
A mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and a surface layer are obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. A mixture of a graft copolymer and an aromatic vinyl polymer, a polymer alloy of polypropylene, and a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in an intermediate layer in the presence of a conjugated diene-based synthetic rubber; It was prepared by co-extrusion molding a three-layer structure sheet made of a resin composition in which a mixture of aromatic vinyl polymers and a crushed product of a resin inner box material consisting of the adhesive layer, surface layer and intermediate layer are mixed. .

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus prepared has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. Graft copolymer obtained by polymerizing a monomer mixture of 5 to 25 wt% vinyl cyanide compound and 75 to 95 wt% aromatic vinyl compound below, and 5 to 25 wt% vinyl cyanide compound A mixture of a copolymer of 75 to 95% by weight of an aromatic vinyl compound has high chemical resistance and prevents HCFC141b of a foaming agent or cyclopentane from penetrating into the resin.
Or with the strong chemical attack of cyclopentane,
60 ° C / -25 without breaking the resin molecular chain
Even when subjected to a thermal shock test of 5 ° C. for 5 cycles, crazes and cracks did not occur.

A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in the surface layer and an aromatic vinyl polymer, and a polymer alloy of polypropylene are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, so it is less likely that the sheet or vacuum-formed product will be damaged. In addition, since it is glossy and has high thermal stability, the appearance performance can be maintained high without discoloring due to heat during sheet extrusion or vacuum forming.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box body having high heat insulating performance can be obtained.

(Embodiment 16) In addition, claim 1 of the present invention
6 will be described. An adhesive layer with a urethane heat insulating material was obtained by polymerizing a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. A graft copolymer,
A mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and a surface layer containing 5 to 25% by weight of a vinyl cyanide compound in the presence of a conjugated diene-based synthetic rubber. Graft copolymer obtained by polymerizing a monomer mixture with ˜95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber as an intermediate layer, the adhesive layer, the surface layer, It was prepared by coextrusion molding a three-layer structure sheet of a resin composition in which a crushed product of a resin inner box material composed of an intermediate layer was mixed.

An inner box formed by vacuum forming this sheet was joined to an outer box made of an iron plate, and a urethane heat insulating material was integrally foamed between both boxes to form a heat insulating box.

Two types of urethane heat insulating materials were used with the same formulation as in the first embodiment. The heat-insulating box body of the present invention thus prepared has good mold reproducibility during vacuum forming as the inner box quality, and the presence of the conjugated diene-based synthetic rubber forming the adhesive layer with the urethane heat insulating material of the inner box. Graft copolymer obtained by polymerizing a monomer mixture of 5 to 25 wt% vinyl cyanide compound and 75 to 95 wt% aromatic vinyl compound below, and 5 to 25 wt% vinyl cyanide compound A mixture of a copolymer of 75 to 95% by weight of an aromatic vinyl compound has high chemical resistance and prevents HCFC141b of a foaming agent or cyclopentane from penetrating into the resin.
Or with the strong chemical attack of cyclopentane,
60 ° C / -25 without breaking the resin molecular chain
Even when subjected to a thermal shock test of 5 ° C. for 5 cycles, crazes and cracks did not occur.

In the presence of the conjugated diene type synthetic rubber for the surface layer, 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack even when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and has excellent appearance performance. I could keep it high.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including an intermediate layer. Even when recycled as an intermediate layer, no crazes or cracks were generated and no deterioration in physical properties was observed in the above thermal cycle test.

Further, the urethane heat insulating material has an excellent fluidity and can evenly fill the space between the inner box and the outer box, so that a heat insulating box having a high heat insulating performance can be obtained.

[0130]

As is apparent from the above description, the heat insulating box body according to claim 1 of the present invention is a heat insulating box made of urethane heat insulating material integrally foamed between the resin inner box and the metal outer box. The urethane heat insulating material is a polyol, a foam stabilizer, a catalyst, HCFC141b or cyclopentane as a foaming agent, 40 to 100% by weight of polymeric MDI or its prepolymerized compound as an isocyanate component, and the remainder is TDI-80, It has a crude TDI and an organic polyisocyanate as a prepolymer thereof, and the resin inner box has an adhesive layer with a urethane heat insulating material in an amount of 50 to 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of methyl methacrylate. A copolymer obtained by polymerizing a monomer mixture of the compounds is prepared, and the surface layer is formed of an aromatic vinyl compound monomer in the presence of a conjugated diene synthetic rubber. A graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber as an intermediate layer, which is a mixture of a graft copolymer obtained by polymerizing a polymer and an aromatic vinyl polymer. Since it has a three-layer structure composed of a resin composition in which a pulverized product of a resin inner box material comprising the adhesive layer, the surface layer and the intermediate layer is mixed, a urethane of the inner box is formed. 50 to 95% by weight of an aromatic vinyl compound constituting an adhesive layer with a heat insulating material and 5 to 5
A copolymer obtained by polymerizing a monomer mixture of 0% by weight of a methyl methacrylate compound is HCFC141b as a foaming agent.
Alternatively, since the permeation of cyclopentane into the resin is prevented, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being broken, so that it is possible to prevent crazes and cracks.

Further, the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer is glossy and also has thermal stability. Since it is expensive, there is an effect that the appearance performance is improved without discoloring due to heat during sheet extrusion or vacuum forming.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber, It is pulverized as it is with a three-layer structure including the intermediate layer and mixed with a mixture of an aromatic vinyl polymer and a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 2 of the present invention comprises a urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, wherein the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the remainder is TDI-80, crude TDI, and an organic polyisocyanate which is a prepolymerized product thereof, and the resin inner box has an adhesive layer of 50 with an urethane heat insulating material.
-95 wt% of an aromatic vinyl compound and 5-50 wt% of a methylmethacrylate compound are mixed to obtain a copolymer, and the surface layer is a conjugated diene compound monomer and an aromatic vinyl compound monomer. A copolymer obtained by polymerizing a monomer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene synthetic rubber in the intermediate layer. Since it has a three-layer structure of a resin composition in which a crushed product of a resin inner box material including the adhesive layer, the surface layer, and the intermediate layer is mixed, the adhesive layer with the urethane heat insulating material of the inner box is formed. A copolymer obtained by polymerizing a monomer mixture of 50 to 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound is HCF as a foaming agent.
Since the permeation of C141b or cyclopentane into the resin is prevented, HCFC141b or cyclopentane has a strong chemical attack property, and the molecular chain of the resin is not broken, so that there is an effect that crazes and cracks can be prevented.

Further, since the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability, the thermal stability at the time of sheet extrusion or vacuum forming is high. There is an effect that the appearance performance is improved without discoloring.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby providing an insulating box body with high heat insulating performance.

The heat insulating box according to claim 3 of the present invention comprises a urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the remainder is TDI-80, crude TDI, and an organic polyisocyanate which is a prepolymerized product thereof, and the resin inner box has an adhesive layer of 50 with an urethane heat insulating material.
-95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a copolymer of monomers obtained by polymerizing a methyl methacrylate compound, the surface layer of which is aromatic vinyl in the presence of a conjugated diene-based synthetic rubber. A mixture of a graft copolymer obtained by polymerizing a compound monomer and an aromatic vinyl polymer, a polymer alloy of polypropylene, an intermediate layer containing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber. A three-layer structure having a resin composition in which a mixture of a graft copolymer obtained by polymerization and an aromatic vinyl polymer and a crushed product of a resin inner box material composed of the adhesive layer, the surface layer and the intermediate layer are mixed Since it is a structure, it forms an adhesive layer with the urethane heat insulating material of the inner box 50 ~
A copolymer obtained by polymerizing a monomer mixture of 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound prevents penetration of HCFC141b or cyclopentane as a foaming agent into the resin. So HCFC14
1b or cyclopentane has a strong chemical attack property, and the molecular chain of the resin is not cut, so that there is an effect that crazes and cracks can be prevented.

The mixture of the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer and the aromatic vinyl polymer, and the polymer alloy of polypropylene are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, and the damage to the sheet or vacuum-formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, there is an effect that the appearance performance is improved without being discolored by heat during sheet extrusion or vacuum forming.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby providing an insulating box body with high heat insulating performance.

The heat insulating box according to claim 4 of the present invention comprises a urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the remainder is TDI-80, crude TDI, and an organic polyisocyanate which is a prepolymerized product thereof, and the resin inner box has an adhesive layer of 50 with an urethane heat insulating material.
A copolymer obtained by polymerizing a monomer mixture of ˜95 wt% of an aromatic vinyl compound and 5˜50 wt% of a methyl methacrylate compound, the surface layer of which is 5 to 25% in the presence of a conjugated diene-based synthetic rubber. 75% to 95% by weight of vinyl cyanide compound
Graft copolymer obtained by polymerizing a monomer mixture with a weight percent of an aromatic vinyl compound, and a vinyl cyanide compound 5
~ 25 wt% and aromatic vinyl compound 75-95 wt% copolymer, graft copolymer obtained by polymerizing aromatic vinyl compound monomer in the middle layer in the presence of conjugated diene-based synthetic rubber Since it has a three-layer structure composed of a resin composition in which a pulverized product of a resin inner box material comprising the adhesive layer, the surface layer and the intermediate layer is mixed, a urethane of the inner box is formed. A copolymer obtained by polymerizing a monomer mixture of 50 to 95% by weight of an aromatic vinyl compound and 5 to 50% by weight of a methyl methacrylate compound, which constitutes an adhesive layer with a heat insulating material, is HCFC141b as a foaming agent. Alternatively, since the permeation of cyclopentane into the resin is prevented and the strong chemical attack of HCFC141b or cyclopentane does not cut the molecular chain of the resin, it is possible to prevent crazes and cracks. There is a cormorant effect.

In the presence of the conjugated diene type synthetic rubber for the surface layer, 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and its appearance performance is high. It has the effect of increasing the cost.

Since the adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box body according to claim 5 of the present invention comprises a urethane heat insulating material integrally foamed between a resin inner box and a metal outer box, wherein the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the remainder is TDI-80, crude TDI and an organic polyisocyanate which is a prepolymer thereof, and the resin inner box has an adhesive layer with a urethane heat insulating material in the presence of a conjugated diene-based synthetic rubber as an aromatic vinyl compound. A mixture of a graft copolymer obtained by polymerizing monomers and an aromatic vinyl polymer, a polymer alloy of polypropylene, and a surface layer of an aromatic vinyl compound monomer are polymerized in the presence of a conjugated diene-based synthetic rubber. A mixture of the graft copolymer and the aromatic vinyl polymer obtained by the polymerization, and an intermediate layer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber, and the graft copolymer and the aromatic vinyl polymer. Since the mixture has a three-layer structure of a resin composition in which a pulverized product of a resin inner box material including the adhesive layer, the surface layer and the intermediate layer is mixed, the urethane of the inner box is A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber that constitutes an adhesive layer with a heat material, and a polymer alloy of polypropylene Since the permeation of HCFC141b or cyclopentane of the foaming agent into the inside of the resin is prevented, the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being cut, and thus crazes and cracks can be prevented. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, there is an effect that a sheet or a vacuum-formed product is less likely to be damaged.

Further, the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber of the surface layer is glossy and also has thermal stability. Since it is expensive, there is an effect that the appearance performance is improved without discoloring due to heat during sheet extrusion or vacuum forming.

Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 6 of the present invention comprises a urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, wherein the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the remainder is TDI-80, crude TDI and an organic polyisocyanate which is a prepolymer thereof, and the resin inner box has an adhesive layer with a urethane heat insulating material in the presence of a conjugated diene-based synthetic rubber as an aromatic vinyl compound. A mixture of a graft copolymer obtained by polymerizing monomers and an aromatic vinyl polymer, a polymer alloy of polypropylene, and a surface layer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer. A copolymer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for the intermediate layer, the adhesive layer, and the surface. Conjugated diene-based compound that forms the adhesive layer with the urethane heat insulating material of the inner box because it has a three-layer structure in which a crushed product of a resin inner box material consisting of two layers and an intermediate layer is mixed A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a polymer, and a polymer alloy of polypropylene are added to the inside of the resin of the blowing agent HCFC141b or cyclopentane. Since the permeation is prevented, HCFC141b or cyclopentane has a strong chemical attack property, and the molecular chain of the resin is not cut, so that crazes and cracks can be prevented. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, there is an effect that a sheet or a vacuum-formed product is less likely to be damaged.

Further, since the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability, the graft copolymer has a high thermal stability, so that it can be heated at the time of sheet extrusion or vacuum forming. There is an effect that the appearance performance is improved without discoloring.

Since the adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 7 of the present invention comprises a urethane heat insulating material integrally foamed between both the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the remainder is TDI-80, crude TDI and an organic polyisocyanate which is a prepolymer thereof, and the resin inner box has an adhesive layer with a urethane heat insulating material in the presence of a conjugated diene-based synthetic rubber as an aromatic vinyl compound. A mixture of a graft copolymer obtained by polymerizing monomers and an aromatic vinyl polymer, a polymer alloy of polypropylene, and a surface layer of an aromatic vinyl compound monomer are polymerized in the presence of a conjugated diene-based synthetic rubber. A graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in a mixture of the graft copolymer and the aromatic vinyl polymer obtained as above, a polypropylene polymer alloy, and an intermediate layer. A mixture of a polymer and an aromatic vinyl polymer, the adhesive layer, the surface layer,
In the presence of the conjugated diene-based synthetic rubber that forms the adhesive layer with the urethane heat insulating material of the inner box, because it has a three-layer structure in which the crushed product of the resin inner box material including the intermediate layer is mixed A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer with an aromatic vinyl polymer, and a polymer alloy of polypropylene are HCFC141 as a foaming agent.
It is possible to prevent the penetration of b or cyclopentane into the resin.

Therefore, due to the strong chemical attack of HCFC141b or cyclopentane, the molecular chain of the resin is not cut, and crazes and cracks can be prevented. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, there is an effect that a sheet or a vacuum-formed product is less likely to be damaged.

The mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber of the surface layer and the polypropylene polymer alloy are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, and the damage to the sheet or vacuum-formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, there is an effect that the appearance performance is improved without being discolored by heat during sheet extrusion or vacuum forming.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has excellent fluidity, and can evenly fill the space between the inner box and the outer box, resulting in an insulating box body having high heat insulating performance.

The heat insulating box according to claim 8 of the present invention comprises a urethane heat insulating material integrally foamed between both the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the remainder is TDI-80, crude TDI and an organic polyisocyanate which is a prepolymer thereof, and the resin inner box has an adhesive layer with a urethane heat insulating material in the presence of a conjugated diene-based synthetic rubber as an aromatic vinyl compound. A mixture of a graft copolymer obtained by polymerizing monomers and an aromatic vinyl polymer, a polymer alloy of polypropylene, and a surface layer containing 5 to 25% by weight of a vinyl cyanide compound in the presence of a conjugated diene-based synthetic rubber And a graft copolymer obtained by polymerizing a monomer mixture of 75 to 95% by weight of an aromatic vinyl compound, a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. A mixture of polymers,
From the adhesive layer, the surface layer, and the intermediate layer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the intermediate layer in the presence of a conjugated diene-based synthetic rubber Since it has a three-layer structure in which a crushed product of a resin inner box material is mixed to form a resin composition, aromatic compounds are present in the presence of a conjugated diene-based synthetic rubber that forms an adhesive layer with the urethane heat insulating material of the inner box. The mixture of the graft copolymer obtained by polymerizing the vinyl compound monomer and the aromatic vinyl polymer and the polymer alloy of polypropylene can prevent the permeation of HCFC141b or cyclopentane of the foaming agent into the resin.

Therefore, the strong chemical attack of HCFC141b or cyclopentane does not break the molecular chain of the resin, so that crazes and cracks can be prevented. Further, since the impact resistance is high and the propagation of cracks is small even if there is a notch, there is an effect that a sheet or a vacuum-formed product is less likely to be damaged.

Further, in the presence of the conjugated diene type synthetic rubber of the surface layer, 5 to 25% by weight of the vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and its appearance performance is high. It has the effect of increasing the cost.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 9 of the present invention comprises a urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol or a foam stabilizer. , Catalyst, HCFC141b or cyclopentane as blowing agent, polymeric M as isocyanate component
40 to 100% by weight of DI or its prepolymerized product
And the balance consists of TDI-80, crude TDI and an organic polyisocyanate as a prepolymerized product thereof, and the resin inner box has an adhesive layer with a urethane heat insulating material in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber. Graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer, and a surface layer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber A mixture of a copolymer and an aromatic vinyl polymer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in an intermediate layer in the presence of a conjugated diene-based synthetic rubber And a three-layer structure of a resin composition in which a crushed product of a resin inner box material consisting of the adhesive layer, the surface layer and the intermediate layer is mixed, the adhesive layer with the urethane heat insulating material of the inner box is formed. Conjugate Graft copolymer in the presence of ene-based synthetic rubber 10-30% by weight obtained by polymerizing an aromatic vinyl compound monomer 70-90% by weight, HCFC blowing agent
Since HCFC141b or cyclopentane absorbs 141b or cyclopentane and prevents the penetration of the foaming agent into the resin, the strong chemical attack property of HCFC141b or cyclopentane prevents the molecular chain of the resin from being broken and prevents the craze and cracking. is there.

Further, the mixture of the graft copolymer and the aromatic vinyl polymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber of the surface layer is glossy and also has thermal stability. Since it is expensive, there is an effect that the appearance performance is improved without discoloring due to heat during sheet extrusion or vacuum forming.

Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 10 of the present invention comprises a urethane heat insulating material integrally foamed between both the resin inner box and the metal outer box, wherein the urethane heat insulating material is a polyol,
HCFC141b or cyclopentane as a foam stabilizer, a catalyst, a foaming agent, 40 to 100% by weight of polymeric MDI or a prepolymerized product thereof as an isocyanate component, and the remainder is TDI-80, crude TDI and an organic polyisocyanate containing the prepolymerized product thereof. A graft obtained by polymerizing an aromatic vinyl compound monomer in an amount of 70 to 90% by weight in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber in the resin inner box for forming an adhesive layer with a urethane heat insulating material. Copolymer, a copolymer obtained by polymerizing the surface layer with a conjugated diene compound monomer and an aromatic vinyl compound monomer,
From the adhesive layer, the surface layer, and the intermediate layer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the intermediate layer in the presence of a conjugated diene-based synthetic rubber Conjugated diene-based synthetic rubbers 10 to 3 that form an adhesive layer with the urethane heat insulating material of the inner box because the resin composition is a mixture of crushed resin inner box materials
Aromatic vinyl compound monomer 70-9 in the presence of 0% by weight
The graft copolymer obtained by polymerizing 0% by weight absorbs the blowing agent HCFC141b or cyclopentane and prevents the blowing agent from penetrating into the resin. Therefore, HCFC141b or cyclopentane has a strong chemical attack property and the resin molecule There is an effect that the chain is not broken and crazes and cracks can be prevented.

Further, since the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability, it has a high thermal stability, so that it is not affected by heat during sheet extrusion or vacuum forming. There is an effect that the appearance performance is improved without discoloring.

Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene type synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 11 of the present invention is made of urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol,
HCFC141b or cyclopentane as a foam stabilizer, a catalyst, a foaming agent, an organic polyisocyanate having 40 to 100% by weight of polymeric MDI or a prepolymerized product thereof as an isocyanate component, and the remainder being TDI-80, crude TDI and a prepolymerized product thereof. A graft obtained by polymerizing an aromatic vinyl compound monomer in an amount of 70 to 90% by weight in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber in the resin inner box for forming an adhesive layer with a urethane heat insulating material. Copolymer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in the surface layer, a polymer alloy of polypropylene, and an intermediate layer Graft Copolymers Obtained by Polymerizing Aromatic Vinyl Compound Monomers in the Presence of Conjugated Diene Synthetic Rubber The inner box has a three-layer structure in which a mixture of a polymer and an aromatic vinyl polymer and a crushed product of a resin inner box material including the adhesive layer, the surface layer, and the intermediate layer are mixed to form a resin composition. The graft copolymer obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber forming an adhesive layer with the urethane heat insulating material is foamed. It absorbs HCFC141b or cyclopentane as the agent and prevents the penetration of the foaming agent into the resin, so the strong chemical attack of HCFC141b or cyclopentane prevents the molecular chain of the resin from being cleaved and prevents crazes and cracks. effective.

The mixture of the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer and the aromatic vinyl polymer, and the polymer alloy of polypropylene are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, and the damage to the sheet or vacuum-formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, there is an effect that the appearance performance is improved without being discolored by heat during sheet extrusion or vacuum forming.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 12 of the present invention is made of urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, wherein the urethane heat insulating material is a polyol,
HCFC141b or cyclopentane as a foam stabilizer, a catalyst, a foaming agent, 40 to 100% by weight of polymeric MDI or a prepolymerized product thereof as an isocyanate component, and the remainder is TDI-80, crude TDI and an organic polyisocyanate containing the prepolymerized product thereof. A graft obtained by polymerizing an aromatic vinyl compound monomer in an amount of 70 to 90% by weight in the presence of 10 to 30% by weight of a conjugated diene-based synthetic rubber in the resin inner box for forming an adhesive layer with a urethane heat insulating material. Copolymer, surface layer in the presence of conjugated diene-based synthetic rubber 5-25 wt% vinyl cyanide compound and 75-
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in a mixture and an intermediate layer in the presence of a conjugated diene-based synthetic rubber, the adhesive layer, the surface layer, and the intermediate layer. 10 to 30 parts by weight of a conjugated diene-based synthetic rubber that forms an adhesive layer with the urethane heat insulating material of the inner box, because the resin composition has a three-layer structure in which a crushed product of a resin inner box material consisting of layers is mixed. %, The graft copolymer obtained by polymerizing 70 to 90% by weight of the aromatic vinyl compound monomer absorbs the blowing agent HCFC141b or cyclopentane and prevents the penetration of the blowing agent into the resin. HCFC14 A strong chemical attack resistant b or cyclopentane, without the molecular chain of the resin is cut, there is an effect that crazing or cracking can be prevented.

In the presence of the conjugated diene-based synthetic rubber for the surface layer, 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and its appearance performance is high. It has the effect of increasing the cost.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 13 of the present invention comprises a urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, wherein the urethane heat insulating material is a polyol,
HCFC141b or cyclopentane as a foam stabilizer, a catalyst, a foaming agent, an organic polyisocyanate having 40 to 100% by weight of polymeric MDI or a prepolymerized product thereof as an isocyanate component, and the remainder being TDI-80, crude TDI and a prepolymerized product thereof. The resin inner box comprises an adhesive layer with a urethane heat insulating material, in the presence of a conjugated diene-based synthetic rubber, a vinyl cyanide compound of 5 to 25% by weight and an aromatic vinyl compound of 75 to 95% by weight. A graft copolymer obtained by polymerizing a monomer mixture, a mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and a surface layer of a conjugated diene-based synthetic rubber. Mixture of graft copolymer and aromatic vinyl polymer obtained by polymerizing aromatic vinyl compound monomer in the presence From the adhesive layer, the surface layer, and the intermediate layer, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the intermediate layer in the presence of a conjugated diene-based synthetic rubber Since it has a three-layer structure of a resin composition obtained by mixing crushed products of the resin inner box material,
A monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound was added in the presence of a conjugated diene-based synthetic rubber forming an adhesive layer with the urethane heat insulating material of the inner box. A mixture of a graft copolymer obtained by polymerization and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound has high chemical resistance,
It is possible to prevent the foaming agent from penetrating the HCFC 141b or cyclopentane into the resin.

Therefore, the strong chemical attack of HCFC141b or cyclopentane has the effect of preventing the molecular chain of the resin from being cut and preventing crazes and cracks.

Further, the mixture of the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer and the aromatic vinyl polymer is glossy and has thermal stability. Since it is expensive, there is an effect that the appearance performance is improved without discoloring due to heat during sheet extrusion or vacuum forming.

Since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 14 of the present invention comprises a urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, wherein the urethane heat insulating material is a polyol,
HCFC141b or cyclopentane as a foam stabilizer, a catalyst, a foaming agent, an organic polyisocyanate having 40 to 100% by weight of polymeric MDI or a prepolymerized product thereof as an isocyanate component, and the remainder being TDI-80, crude TDI and a prepolymerized product thereof. The resin inner box comprises an adhesive layer with a urethane heat insulating material, in the presence of a conjugated diene-based synthetic rubber, a vinyl cyanide compound of 5 to 25% by weight and an aromatic vinyl compound of 75 to 95% by weight. A graft copolymer obtained by polymerizing a monomer mixture, a mixture of a copolymer of vinyl cyanide compound of 5 to 25% by weight and an aromatic vinyl compound of 75 to 95% by weight, a surface layer of which is a conjugated diene compound monomer. A copolymer obtained by polymerizing a vinyl aromatic compound and an aromatic vinyl compound monomer, and the intermediate layer in the presence of a conjugated diene-based synthetic rubber. A resin obtained by mixing a mixture of a graft copolymer obtained by polymerizing a group vinyl compound monomer and an aromatic vinyl polymer, and a crushed product of a resin inner box material including the adhesive layer, the surface layer and the intermediate layer. Since the composition is a three-layer structure, 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of a vinyl cyanide compound in the presence of a conjugated diene-based synthetic rubber forming an adhesive layer with the urethane heat insulating material of the inner box % Of a vinyl vinyl compound and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. It has high chemical resistance and can prevent the permeation of HCFC141b or cyclopentane of the foaming agent into the resin.

Therefore, due to the strong chemical attack of HCFC141b or cyclopentane, the molecular chain of the resin is not cut, and crazes and cracks can be prevented.

Further, since the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber of the surface layer has high thermal stability, the graft copolymer has a high heat stability during sheet extrusion and vacuum forming. There is an effect that the appearance performance is improved without discoloring.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 15 of the present invention is made of urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol,
HCFC141b or cyclopentane as a foam stabilizer, a catalyst, a foaming agent, an organic polyisocyanate having 40 to 100% by weight of polymeric MDI or a prepolymerized product thereof as an isocyanate component, and the remainder being TDI-80, crude TDI and a prepolymerized product thereof. The resin inner box comprises an adhesive layer with a urethane heat insulating material, in the presence of a conjugated diene-based synthetic rubber, a vinyl cyanide compound of 5 to 25% by weight and an aromatic vinyl compound of 75 to 95% by weight. A graft copolymer obtained by polymerizing a monomer mixture, a mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and a surface layer of a conjugated diene-based synthetic rubber. Mixture of graft copolymer and aromatic vinyl polymer obtained by polymerizing aromatic vinyl compound monomer in the presence of A polymer alloy of polypropylene, a mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in an intermediate layer, and the adhesive layer, Surface layer,
In the presence of the conjugated diene-based synthetic rubber that forms the adhesive layer with the urethane heat insulating material of the inner box, because it has a three-layer structure in which the crushed product of the resin inner box material including the intermediate layer is mixed 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and HCF as a foaming agent.
It is possible to prevent the penetration of C141b or cyclopentane into the resin.

Therefore, due to the strong chemical attack of HCFC141b or cyclopentane, the molecular chain of the resin is not cut, and crazes and cracks can be prevented.

A mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber for the surface layer and an aromatic vinyl polymer, and a polymer alloy of polypropylene are resistant to each other. The impact resistance is high, and even if there is a notch, the propagation of cracks is small, and the damage to the sheet or vacuum-formed product is unlikely to occur. Further, since it is glossy and has high thermal stability, there is an effect that the appearance performance is improved without being discolored by heat during sheet extrusion or vacuum forming.

Further, since the adhesive layer and the surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber, It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

The heat insulating box according to claim 16 of the present invention is made of urethane heat insulating material integrally foamed between the resin inner box and the metal outer box, and the urethane heat insulating material is a polyol,
HCFC141b or cyclopentane as a foam stabilizer, a catalyst, a foaming agent, 40 to 100% by weight of polymeric MDI or a prepolymerized product thereof as an isocyanate component, and the remainder is TDI-80, crude TDI and an organic polyisocyanate containing the prepolymerized product thereof. The resin inner box comprises an adhesive layer with a urethane heat insulating material, in the presence of a conjugated diene-based synthetic rubber, a vinyl cyanide compound of 5 to 25% by weight and an aromatic vinyl compound of 75 to 95% by weight. A graft copolymer obtained by polymerizing a monomer mixture, a mixture of a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and a surface layer of a conjugated diene-based synthetic rubber. Monomer in the presence of 5 to 25% by weight vinyl cyanide compound and 75 to 95% by weight aromatic vinyl compound Of a graft copolymer obtained by polymerizing a compound, a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound, and an intermediate layer containing a conjugated diene-based synthetic rubber Below, a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer and an aromatic vinyl polymer, and a crushed product of a resin inner box material comprising the adhesive layer, surface layer and intermediate layer are prepared. Since it has a three-layer structure as a mixed resin composition, 5 to 25% by weight of a vinyl cyanide compound and 75% by weight of a vinyl cyanide compound are used in the presence of a conjugated diene-based synthetic rubber forming an adhesive layer with the urethane heat insulating material of the inner box. ~ 95% by weight of a graft copolymer obtained by polymerizing a monomer mixture with an aromatic vinyl compound, and a vinyl cyanide compound
A mixture of a copolymer of 25% by weight and an aromatic vinyl compound of 75 to 95% by weight has high chemical resistance and is a blowing agent HCFC14.
It is possible to prevent the penetration of 1b or cyclopentane into the resin.

Therefore, due to the strong chemical attack of HCFC141b or cyclopentane, the molecular chain of the resin is not cut, and crazes and cracks can be prevented.

In the presence of the conjugated diene-based synthetic rubber for the surface layer, 5 to 25% by weight of a vinyl cyanide compound and 75 to
A graft copolymer obtained by polymerizing a monomer mixture with 95% by weight of an aromatic vinyl compound, and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. The mixture has high chemical resistance and does not easily crack when it comes into contact with edible oil.It also has gloss and high thermal stability, so it does not discolor due to heat during sheet extrusion or vacuum forming, and its appearance performance is high. It has the effect of increasing the cost.

The adhesive layer and surface layer with the urethane heat insulating material have high compatibility with the graft copolymer obtained by polymerizing the aromatic vinyl compound monomer in the presence of the conjugated diene-based synthetic rubber. It is mixed with a mixture of a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber and an aromatic vinyl polymer by pulverizing the three-layer structure including the intermediate layer. It has the effect that it can be recycled and used as an intermediate layer. The urethane heat insulating material has an excellent fluidity, and can evenly fill the space between the inner box and the outer box, thereby obtaining an insulating box body having high heat insulating performance.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-103387 (JP, A) JP-A-7-242766 (JP, A) JP-A-6-159919 (JP, A) JP-A-5- 320463 (JP, A) JP-A-3-45881 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) F25D 23/08

Claims (16)

(57) [Claims] 1. A heat insulating box body made of urethane heat insulating material integrally foamed between a resin inner box and a metal outer box.
The urethane heat insulating material is a polyol, a foam stabilizer, a catalyst, HCFC141b or cyclopentane as a foaming agent, and polymeric MDI or its prepolymerized compound as an isocyanate component is 40 to 100% by weight, and the rest is TD
I-80, crude TDI and an organic polyisocyanate as a prepolymerized product thereof, wherein the resin inner box has a three-layer structure including an adhesive layer, a surface layer and an intermediate layer, and the urethane heat insulating material is adhered to the inner layer. 50-95% by weight of adhesive layer
A copolymer obtained by polymerizing a monomer mixture of the aromatic vinyl compound of 5 to 50% by weight of a methyl methacrylate compound, the surface layer of which is an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. A graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber as an intermediate layer, which is a mixture of a graft copolymer obtained by polymerizing a polymer and an aromatic vinyl polymer. And a vinyl aromatic polymer mixture, and a heat-insulated box body made of a resin composition in which a crushed product of a resin inner box material comprising the adhesive layer, the surface layer, and the intermediate layer is mixed. 2. A heat insulation box body, wherein the surface layer according to claim 1 is a copolymer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer. 3. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the surface layer according to claim 1 in the presence of a conjugated diene-based synthetic rubber, and polypropylene. A heat insulating box body characterized by being a polymer alloy of. 4. The surface layer according to claim 1, wherein a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound is present in the presence of a conjugated diene-based synthetic rubber. A heat-insulating box, which is a mixture of a graft copolymer obtained by polymerization and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. 5. A graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber to form an adhesive layer for adhering to the urethane heat insulating material according to claim 1, and an aromatic vinyl polymer. A heat-insulating box body characterized by being a mixture of coalescing and a polymer alloy of polypropylene. 6. A graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber to form an adhesive layer for adhering to the urethane heat insulating material according to claim 2, and an aromatic vinyl polymer. A heat-insulating box body characterized by being a mixture of coalescing and a polymer alloy of polypropylene. 7. A graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber to form an adhesive layer for adhering to the urethane heat insulating material according to claim 3, and an aromatic vinyl polymer. A heat-insulating box body characterized by being a mixture of coalescing and a polymer alloy of polypropylene. 8. The surface layer according to claim 7, wherein a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound is used in the presence of a conjugated diene-based synthetic rubber. A heat insulating box, comprising a graft copolymer obtained by polymerization and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. 9. An adhesive layer for adhering to the urethane heat insulating material according to claim 8, obtained by polymerizing 70 to 90% by weight of an aromatic vinyl compound monomer in the presence of 10 to 30% by weight of a conjugated diene synthetic rubber. And a graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in the surface layer, and a mixture of the aromatic vinyl polymer and the graft copolymer. Insulated box body. 10. A heat insulation box body, wherein the surface layer according to claim 9 is a copolymer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer. 11. A mixture of a graft copolymer and an aromatic vinyl polymer obtained by polymerizing an aromatic vinyl compound monomer in the surface layer according to claim 10 in the presence of a conjugated diene-based synthetic rubber, and polypropylene. A heat insulating box body characterized by being a polymer alloy of. 12. The surface layer according to claim 11, wherein a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound is used in the presence of a conjugated diene-based synthetic rubber. A heat insulating box, comprising a graft copolymer obtained by polymerization and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound. 13. An adhesive layer for adhering to the urethane heat insulating material according to claim 12, comprising 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound in the presence of a conjugated diene-based synthetic rubber. Graft copolymer obtained by polymerizing the monomer mixture of
Graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in the surface layer, which is a mixture of a copolymer of 25% by weight and an aromatic vinyl compound 75 to 95% by weight. A heat-insulating box body, characterized in that it is a mixture of styrene and an aromatic vinyl polymer. 14. A heat insulating box, wherein the surface layer according to claim 13 is a copolymer obtained by polymerizing a conjugated diene compound monomer and an aromatic vinyl compound monomer. 15. An adhesive layer for adhering to the urethane heat insulating material according to claim 14, wherein 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound are present in the presence of a conjugated diene-based synthetic rubber. Graft copolymer obtained by polymerizing the monomer mixture of
Graft copolymer obtained by polymerizing an aromatic vinyl compound monomer in the presence of a conjugated diene-based synthetic rubber in the surface layer, which is a mixture of a copolymer of 25% by weight and an aromatic vinyl compound 75 to 95% by weight. A heat-insulating box body comprising a polymer alloy of polypropylene and a mixture of aromatic vinyl polymer. 16. The surface layer according to claim 15, wherein a monomer mixture of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound is used in the presence of a conjugated diene-based synthetic rubber. A heat insulating box, comprising a graft copolymer obtained by polymerization and a copolymer of 5 to 25% by weight of a vinyl cyanide compound and 75 to 95% by weight of an aromatic vinyl compound.