JP3478810B2 - Insulated box, raw material manufacturing method, and refrigerator - 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 made of hard urethane foam and a vacuum heat insulating material, a method for manufacturing a raw material of hard urethane foam, and a refrigerator.

[0002]

2. Description of the Related Art In recent years, various efforts have been made to save energy and resources from the viewpoint of protecting the global environment.

From the viewpoint of energy saving, there is a technique in which a vacuum heat insulating material is disposed between an inner box and an outer box of a heat insulating box and integrally foamed with a rigid urethane foam to form a box with high heat insulating performance. No. 57-96852.

Further, from the viewpoint of resource saving, the recycling of waste home electric appliances such as refrigerators and televisions has become an extremely important theme, and various efforts have been made especially for refrigerators.

Metal materials such as iron plates can be relatively easily recycled for the recycling of refrigerators, especially for the heat insulating box which is the main component. However, although plastics, especially hard urethane foam, which is a thermosetting resin, is used in large quantities as a heat insulating material, it is impossible to melt and regenerate, and in general, landfill or incineration,
Often used as a filler. Under these circumstances, as a recent technique, a process technique has been proposed in which supercritical water or subcritical water is used as a treatment medium to decompose a polymer material.

For example, as disclosed in Japanese Unexamined Patent Publication No. 10-310663, a method for decomposing and recovering a polyurethane resin is to chemically decompose it with water in a supercritical state or a subcritical state, and to use it as a raw material compound of a polyurethane resin or a usable compound. It has been proposed to recover such raw material derivatives.

Further, in Japanese Patent No. 2885673,
It is an attempt to chemically decompose a polymer material using water in a supercritical state or a subcritical state to decompose it into oil.

[0008]

However, as the demand for energy saving increases, it is necessary to increase the use area of the vacuum heat insulating material, that is, the coverage of the vacuum heat insulating material on the surface of the outer box to improve the heat insulating performance. Has become.

There is no problem if the covering rate is about 30% to 40% as in the conventional case, but if the covering rate is further increased, there is a problem that the strength of the heat insulating box as the structure remarkably decreases. It was That is, since the rigid urethane foam forms an integral bond between the outer box and the inner box, the rigidity and strength of the heat insulating box is maintained, but the vacuum heat insulating material of foreign matter occupies a wide portion of the heat insulating wall layer. Moreover, since the thickness of the rigid urethane foam itself becomes thin, the rigidity and strength of the rigid urethane foam alone may cause the thermal insulation box body to be distorted or deformed.

In particular, when the number of doors increases, the door tightness is poor due to distortion, and there is a problem that the heat insulation performance is deteriorated due to a gap in the gasket portion.

For this reason, generally, there is a method in which the density of the rigid urethane foam is significantly increased to increase the flexural modulus which represents the rigidity, but when the density is significantly increased, the solid heat conduction adversely affects the hardness. There is a serious problem that the heat insulation performance of the urethane foam is extremely deteriorated and the originally intended high heat insulation performance of the heat insulation box cannot be obtained.

Further, as the coverage of the vacuum heat insulating material is increased, the heat absorption amount of the heat insulating box is reduced, which leads to energy saving, but naturally the degree of its effect is reduced by drawing a saturation curve, and the investment cost and the cost of the effect are reduced. This results in a loss of rationality in terms of effectiveness.

Further, if it is attempted to increase the coverage more than necessary, it is necessary to provide a vacuum heat insulating material having a size and shape that deviates from the standard, or to install even in a place that is difficult to provide in the manufacturing process. There is a problem in that the cost of the vacuum heat insulating material and the manufacturing cost increase significantly.

Further, in the multi-layer heat insulating part of the rigid urethane foam and the vacuum heat insulating material, if the wall thickness filled with the rigid urethane foam cannot be secured sufficiently, the fluidity of urethane at the time of foaming is lowered and the foam becomes rough. Insufficient filling occurs or the heat insulation performance of the urethane part deteriorates. For this reason, there are cases where the heat insulation performance as a multilayer heat insulation material cannot be achieved as designed, or the heat insulation performance may be deteriorated on the contrary. There is a problem that the tendency tends to increase because most of the urethane layer does not flow easily.

Furthermore, when the heat insulating performance of the vacuum heat insulating material itself is not sufficient, the heat insulating performance of the urethane portion of the multi-layer heat insulating layer is deteriorated, and even if the coverage of the vacuum heat insulating material is sufficiently increased, it is large. There is also a problem that it is difficult to obtain the energy saving effect.

On the other hand, from the viewpoint of resource saving and recycling, rigid urethane foam is disclosed in Japanese Patent Laid-Open No. 10-3106.
By utilizing the technique disclosed in Japanese Patent Laid-Open No. 63, it is possible to recover a raw material compound of a polyurethane resin or an available raw material derivative in a short time.

However, when treating the rigid urethane foam of the heat insulation box, which is a constituent of a used refrigerator,
Even if the product is treated with supercritical water, the hard urethane foam covered with the iron plate of the outer box or the ABS resin of the inner box cannot be chemically decomposed. In addition, various polymeric materials such as polypropylene resin used for interior parts can also be chemically decomposed with supercritical water or subcritical water, so they are generated when they are chemically decomposed in a mixed state. Since various low molecular weight materials are dissolved as impurities in the raw material mixture, there is a problem that they cannot be reused as a rigid urethane foam raw material.

Therefore, for the purpose of industrial recycling, in order to recover the raw material of the polyurethane resin and the usable raw material derivative, in order to recover the raw material of the polyurethane resin and the used waste heat insulating box, a hard material containing no foreign material or impurities is used. Taking out urethane foam was more important than anything else. In addition, the construction of a waste treatment method that separates and collects iron and can be recycled as a whole system at a high recycling rate was a fundamental issue.

Another problem is that the raw material compound of the polyurethane resin obtained by chemical decomposition and the usable raw material derivative are determined by the chemical structure of the rigid urethane foam which is the substance to be decomposed. The point is that it depends on the raw materials used to manufacture the original rigid urethane foam. Therefore, it is important to select the raw material manufacturing method according to the constituent raw materials at the time of manufacturing the original rigid urethane foam.

Furthermore, it was an important task in achieving recycling that the raw material compound of the polyurethane resin obtained by chemical decomposition and the available raw material derivative were used as a heat insulating material for refrigerators. .

Further, if the raw material type of the rigid urethane foam used in the heat insulating box, which is a main component of the waste refrigerator, is unknown, it is not possible to select and determine a suitable treatment method or raw material manufacturing method, which leads to recycling. There was a problem that had the fatal problem that it could not be done.

In view of the above problems, the present invention provides a heat-insulating box body having high box-insulating performance with no problem in box strength even when a large amount of vacuum heat-insulating material is used, and at the same time, recycling of used heat-insulating box material. To improve recycling rate and contribute to recycling, manufacturing method of recycled raw materials, heat insulation box using recycled raw materials,
And a refrigerator is provided.

[0023]

To achieve this object, the present invention has the following configuration.

The heat insulating box according to claim 1 of the present invention has a flexural modulus of 8.0 MPa or more and a density of 60 kg / m.
^A hardness of ³ or less is made of a rigid urethane foam that ensures rigidity and heat insulation performance, and a vacuum heat insulating material, and the coverage of the vacuum heat insulating material exceeds 50% of the surface area of the outer box.

According to the present invention, since the bending elastic modulus of the rigid urethane foam is 8.0 MPa or more, there is no problem in the strength of the box body, and the box body is deformed because it cannot withstand the strain due to the weight of the stored items. There is no problem.

In addition, the density of the rigid urethane foam is increased to increase the rigidity, but the density is 60 kg / m ³
Since it is as follows, there is no deterioration in the heat insulation performance due to the effect of increasing the solid heat conduction. Therefore, even if a large amount of vacuum heat insulating material is used, there is no problem in the quality of the heat insulating box body, and energy saving can be realized by excellent heat insulating performance.

The heat-insulating box body according to claim 2 of the present invention is bent.
Elastic modulus is 8.5-10.0 MPa and density is 45-
55 kg / m3 hard urethane foam and vacuum insulation
The vacuum insulating material has a coverage of 50% of the outer surface area of the outer box.
%.

According to the present invention, a rigid urethane foam of
Bending elastic modulus has a range of 8.5 to 10.0 MPa
Therefore, there is no problem with the box strength, and distortion due to the weight of the stored items
Fully not box body withstand the there is no problem such as deformation.

In addition, a hard urethane foam is added to increase rigidity.
The form density is high, but the density is 45 to 55 kg.
Since the range is / m3, there is an increase in solid heat conduction.
There is no reduction in heat insulation performance. Therefore, a large amount of vacuum insulation material
The quality of the insulation box does not matter even when used for
Energy saving can be realized by thermal performance.

The heat insulating box according to claim 3 of the present invention has a flexural modulus of 8.0 MPa or more and a density of 60 kg / m.
^A hardness of ³ or less is made of a rigid urethane foam that secures rigidity and heat insulation performance, and a vacuum heat insulating material, and the coverage of the vacuum heat insulating material exceeds 40% of the surface area of the outer box and has three or more doors.

According to the present invention, even if the coverage of the vacuum heat insulating material exceeds 40% of the surface area of the outer box and the number of doors is 3 or more, the flexural modulus of the rigid urethane foam is 8.0 MPa.
Since it has the above, there is no problem in the strength of the box, and there is no problem that the box is deformed because it cannot withstand the distortion due to the weight of the stored items. Even if the number of doors that require rigidity is three or more, there is no deformation. The density of the rigid urethane foam is increased to increase the strength, but the density is 60 kg / m ³
Since it is as follows, there is no deterioration in heat insulation performance due to the effect of increasing solid heat conduction. Therefore, even if a large amount of vacuum heat insulating material is used, there is no problem in the quality of the heat insulating box body, and energy saving can be realized by excellent heat insulating performance.

The heat insulating box body according to claim 4 of the present invention is a bent box body.
Elastic modulus is 8.5-10.0 MPa and density is 45-
55 kg / m3 hard urethane foam and vacuum insulation
And the coverage of the vacuum insulation material is 40% of the outer surface area of the outer box.
%, And has three or more doors.

According to the present invention, the coverage of the vacuum heat insulating material is
Over 40% of the box surface area and more than 3 doors
Also, the flexural modulus of rigid urethane foam is 8.5 to 1
Box strength is a problem because it has a range of 0.0 MPa
The box body is deformed because it cannot withstand the distortion due to the weight of the stored items.
There is no problem such as doing. The number of doors that require rigidity is 3
Even if there are more than one sheet, there is no deformation. In addition, for strength improvement
Therefore, the density of rigid urethane foam is increased, but the density is
Since it is in the range of 45 to 55 kg / m3, solid heat
There is no reduction in heat insulation performance due to the effect of increased conduction. Therefore,
Even if a large amount of vacuum insulation material is used, there is a problem with the quality of the insulation box.
Save energy with excellent heat insulation performance without any problem
You can do it.

In the heat insulation box according to claim 5 of the present invention, the rigid urethane foam is prepared by mixing and reacting an isocyanate component composed of a tolylene diisocyanate composition with a premix component composed of a polyol, a foam stabilizer, a catalyst and a foaming agent. It is characterized in that it is obtained.

According to the present invention, since tolylene diisocyanate is used as a raw material for rigid urethane foam,
A resin having a high elastic modulus can be obtained because the reactive groups are close to each other via the aromatic ring. Therefore, it is not necessary to increase the density extremely, the solid heat conduction is not adversely affected, and excellent heat insulation performance can be maintained.

Therefore, even a heat insulating box body having a vacuum heat insulating material covering more than 50% of the surface area of the outer box can exhibit both strength and high heat insulating performance.

Further, even in the case of a heat-insulating box body having a vacuum heat-insulating material covering more than 40% of the outer box surface area and having three or more doors, strength and high heat-insulating performance can be exhibited together. is there.

In the heat-insulating box body according to the sixth aspect of the present invention, the foaming agent of the rigid urethane foam constituting the heat-insulating box body is made of water.

According to the present invention, by using water as a foaming agent, carbon dioxide gas is generated by the reaction with isocyanate to provide for foaming, and at the same time, a strong reaction bond is formed in the resin molecular structure due to its small molecular weight. Form. Therefore, it is not necessary to increase the density extremely, the solid heat conduction is not adversely affected, and excellent heat insulation performance can be maintained. Therefore, even a heat-insulating box body having a vacuum heat-insulating material covering more than 50% of the surface area of the outer box can exhibit both strength and high heat-insulating performance.

Further, since the gas released from the rigid urethane foam at the time of disposal is only carbon dioxide gas, it has an advantage that it can be safely handled even if it is crushed.

Further, even in the case of a heat insulating box having a vacuum heat insulating material covering more than 40% of the surface area of the outer box and having three or more doors, strength and high heat insulating performance can be exhibited together. .

Further, since the gas released from the rigid urethane foam at the time of disposal is only carbon dioxide gas, it has an advantage that it can be safely handled even if it is crushed.

The raw material manufacturing method according to claim 7 of the present invention is
A crushing step of crushing the heat-insulating box according to any one of claims 1 to 6 , and a sorting process in which waste pieces crushed by this crushing step are introduced and sorted into iron, non-ferrous metal, resin dust and the like. Step, a foamed insulation material treatment step in which a rigid urethane foam mass separated from waste in the crushing step is subjected to a powdering treatment by grinding, compression, etc., and a rigid urethane foam powder obtained in the foamed insulation material treatment step Is liquefied by an aminolysis reaction or a glycolysis reaction, etc., and resin fine particles or fine particles of ground metal that become impurities are removed by a filter, and then a chemical treatment operation by a reaction with supercritical water or subcritical water is performed to produce hard urethane foam. The raw material group produced by the waste treatment method consisting of the raw material compound and a re-raw material production step of decomposing into a plurality of amines is fractionally distilled in the raw material production step, From tolylenediamine as one of the distillate component is to synthesize a tolylene diisocyanate composition and tolylenediamine-based polyether polyol.

According to the present invention, the rigid urethane foam made of the tolylene diisocyanate composition as a raw material can be industrially recycled as a raw material for the rigid urethane foam again. In particular, the raw material group obtained by treatment with supercritical water or subcritical water is fractionally distilled to obtain tolylenediisocyanate composition and tolylenediamine-based polyether polyol synthesized from tolylenediamine, which is one of the fractional components. It can be easily synthesized as a raw material for the production of rigid urethane foam and recycled.

The heat-insulating box according to claim 8 of the present invention contains the tolylene diisocyanate composition or tolylene diamine-based polyether polyol polyether polyol obtained in claim 7 as a main raw material and is used as an auxiliary agent. Foaming agent, catalyst,
A foaming agent or the like is mixed and injected between an inner box and an outer box, and foamed and hardened to form a hard urethane foam.

According to the present invention, by reusing the raw material for the rigid urethane foam obtained by decomposing and synthesizing the rigid urethane foam using the tolylene diisocyanate composition as the raw material, the heat-insulating box body which enables resource saving. Can be manufactured.

In the future, when a used heat-insulating box is used, it can be reused as a resource.

On the other hand, the refrigerator according to claim 9 of the present invention comprises:
The material type of rigid urethane foam is displayed. Further, the refrigerator according to claim 10 of the present invention records the raw material type of the rigid urethane foam.

According to the present invention, since the raw material type of the rigid urethane foam used in the heat insulating box, which is a main component of the waste refrigerator, can be determined, it is possible to select and determine a suitable treatment method and raw material manufacturing method, Resources can be easily recycled. Further, by recording the information, it is possible to decide the treatment of the rigid urethane foam by reading the recorded information when the waste is treated in the refrigerator.

A heat insulating box body according to claim 11 of the present invention has a vacuum heat insulating material having a coverage of more than 50% and less than 80% of the outer surface area of the outer box, a bending elastic modulus of 8.0 MPa or more, and a density.
Of 60 kg / m3 or less ensures rigidity and heat insulation performance
A heat-insulating main body consisting of the rigid urethane foam, which said vacuum heat insulator is made of a gas barrier film covering the core material and core material, the core material is made of sheet-shaped inorganic fiber aggregate of a plurality layers Is.

According to the present invention, the energy saving effect can be enhanced by the coverage of the vacuum heat insulating material exceeding 50% of the surface area of the outer box. By keeping the coverage rate at 80% or less, the effect of using a large amount of vacuum heat insulating material is not saturated, and the use of a non-standard form of vacuum heat insulating material or the distribution to areas with poor work efficiency It is possible to prevent the investment effect from significantly lowering during construction work.

Further, by using the inorganic fiber as the core material, generation of gas with time in the vacuum heat insulating material is small and the heat insulating performance can be maintained for a long time. In addition, when manufacturing the vacuum heat insulating material, the step of first filling the inner bag with the powder as in the case of using the powder as the core material is omitted, which improves the production efficiency and the working environment.

Further, since the sheet-shaped core material is used, it can be easily used by adjusting the thickness to two layers or more so that the rigid urethane foam has a fluidized thickness and a multilayer insulation wall. It is possible to effectively enhance the heat insulating property of.

Further, since it is sheet-shaped and has high flatness and good adhesion to the outer box, the foaming agent at the time of foaming the rigid urethane foam aggregates in the gap between the vacuum heat insulating material and the outer box, and the environmental temperature It is possible to suppress deformation of the surface of the outer box due to expansion and contraction due to changes.

The heat insulating box according to claim 12 of the present invention is
True when the coverage is more than 50% and less than 80% of the outer box surface area
Air insulation and flexural modulus of 8.5-10.0MPa,
Hard urethane foam with a density of 45 to 55 kg / m3
And a vacuum insulation material and a core material.
Consisting of a gas barrier film covering the core material,
The core material consists of multiple layers of sheet-like inorganic fiber aggregates.
is there.

According to the present invention, the coverage of the vacuum heat insulating material is
Energy saving effect by exceeding 50% of the box surface area
The fruit can be raised. And the coverage is 80% or less
By using a large amount of vacuum insulation material
The effect of going is not saturated, and a non-standard form of vacuum break
Investment is effective in the use of heat materials and installation work in areas where work efficiency is poor
It is possible to prevent the fruit from significantly lowering.

Further , by using an inorganic fiber as a core material, vacuum break
Long-term insulation performance with less gas generation in the heat material over time
Can be maintained for a period. In addition, when manufacturing the vacuum insulation material, the powder core
First, enclose the powder in the inner bag as when using it as a material.
The process is also omitted, which improves production efficiency and work environment.
It

Whether a sheet-shaped core material is used
Et al., That are use to adjust the thickness required in the two or more layers
Easy to do and secure the flow thickness of rigid urethane foam
While effectively increasing the heat insulation of the multi-layer insulation wall
It

Further , since it is in the form of a sheet, it has high flatness and
Due to the good adhesion with the box, there is a gap between the vacuum insulation and the outer box.
When the rigid urethane foam is foamed,
Deformation occurs on the surface of the outer box due to expansion and contraction due to changes in boundary temperature
Can be suppressed.

The heat insulating box body according to claim 13 of the present invention has vacuum heat insulating materials arranged on both sides, the top surface, the back surface, the bottom surface, and the front surface.

According to the present invention, the vacuum heat insulating material is arranged on all of the six basic surfaces of the heat insulating box, and the coverage of the vacuum heat insulating material exceeds 50% of the outer box surface area and is 80% or less. it can.

According to a fourteenth aspect of the present invention, the heat insulating box has a heat insulating wall thickness of 20 mm to 50 mm except for a door made of hard urethane foam and a vacuum heat insulating material.

According to the present invention, a composite heat insulating wall with a vacuum heat insulating material can be constructed in a range where the fluidity of the rigid urethane foam can be maintained, and the volumetric efficiency of the inner volume with respect to the outer volume of the heat insulating box can be enhanced. .

According to a fifteenth aspect of the present invention, there is provided a heat insulation box body having a thickness of a heat insulation wall excluding a door formed of hard urethane foam and a vacuum heat insulation material in a region where the temperature inside the heat insulation box body is maintained at a freezing temperature. All are 20 mm-50 mm.

According to the present invention, a multi-layer heat insulating wall with a vacuum heat insulating material in the freezing temperature region can be formed within the range where the fluidity of the rigid urethane foam can be maintained, and the content of the heat insulating box body against the outer volume in the freezing temperature region can be improved. The volumetric efficiency of the product can be increased.

According to a sixteenth aspect of the present invention, there is provided a heat insulating box body having a thickness of a heat insulating wall excluding a door formed of a hard urethane foam and a vacuum heat insulating material in a region where the temperature inside the heat insulating box is maintained at a refrigerating temperature. All are 20 mm-40 mm.

According to the present invention, a composite heat insulating wall with a vacuum heat insulating material in the refrigerating temperature region can be formed within a range where the fluidity of the rigid urethane foam can be maintained, and the inner volume of the heat insulating box body with respect to the outer volume in the refrigerating temperature region can be formed. The volumetric efficiency of can be increased.

According to the seventeenth aspect of the present invention, in the heat insulation box body, the vacuum heat insulation material has a thickness of 10 mm to 20 mm.

According to the present invention, the vacuum heat insulating material can be disposed on the portion where the wall thickness is relatively thin while maintaining the fluidity of the rigid urethane foam, and the coverage can be effectively increased.

In the heat-insulating box according to claim 18 of the present invention, the heat conductivity of the vacuum heat insulating material is 0.0010 W / m when the heat conductivity of the rigid urethane foam is 0.015 W / mK.
As K to 0.0030 W / mK, the ratio is 1/15 to 1/5.

According to the present invention, in the case where the thickness of the multi-layered heat insulating wall of the rigid urethane foam and the vacuum heat insulating material is thin, the thickness of the vacuum heat insulating material is reduced in order to secure a thickness that does not impair the fluidity of the rigid urethane foam. Even so, the heat insulation performance as a multi-layer heat insulation wall can be maintained.

The heat insulating box according to claim 19 of the present invention is one in which a vacuum heat insulating material is embedded and arranged in a hard urethane foam between the outer and inner boxes.

According to the present invention, the entire outer surface of the vacuum heat insulating material is in close contact with the hard urethane foam, and the strength of the heat insulating box can be increased. Further, the substantial coverage can be reasonably increased as compared with the case where the vacuum heat insulating material is attached to the outer box.

[0074] insulation box body according to claim 20 of the present invention is to disposed embedded in rigid urethane foam at an intermediate outer box and the inner box and the vacuum heat insulating material on the side surface of the insulating box body, before
An outer box if vacuum insulation is installed on the door, back, or bottom
It is arranged in .

According to the present invention, since the side surface of the outer box and the vacuum heat insulating material do not come into direct contact with each other, the foaming agent of the hard urethane foam aggregates in the gap between the outer box and the vacuum heat insulating material, and expands and contracts due to the change of the environmental temperature. It does not deform the outer box.

[0076] refrigerator according to claim 21 of the present invention, cooling for cooling the heat-insulating main body of any one of claims 11 20, a cooling chamber formed in said heat-insulating main body, said cooling chamber It consists of a device.

According to the present invention, a refrigerator in which a heat insulating box having a high coverage of the vacuum heat insulating material with respect to the surface area of the outer box is rationally realized, and a refrigerator having a high energy saving effect can be provided.

[0078]

BEST MODE FOR CARRYING OUT THE INVENTION The heat-insulating box according to claim 1 of the present invention has a bending elastic modulus of 8.0 MPa or more and a density of 6
It is composed of a rigid urethane foam and a vacuum heat insulating material, which have a rigidity strength and a heat insulating property of 0 kg / m ³ or less.

Further, the coverage of the vacuum heat insulating material exceeds 50% of the surface area of the outer box. Even if the coverage of the vacuum heat insulating material exceeds 50% of the surface area of the outer box, the bending elastic modulus of the rigid urethane foam is 8.0 MPa or more,
There is no problem with the strength of the box, and there is no problem with the box deforming because it cannot withstand the distortion due to the weight of the stored items. In addition, the density of the rigid urethane foam is increased in order to increase the rigidity, but since the density is 60 kg / m ³ or less, there is no deterioration of the heat insulation performance due to the effect of increasing the solid heat conduction. Therefore,
Even if a large amount of vacuum heat insulating material is used, there is no problem in the quality of the heat insulating box body, and energy saving can be realized by excellent heat insulating performance.

The heat insulating box according to claim 2 of the present invention is
Elastic modulus is 8.5 to 10.0 MPa, and density is 45
~ 55kg / m3 rigid urethane foam and vacuum insulation
Consists of.

Further , the coverage ratio of the vacuum heat insulating material depends on the surface area of the outer box.
It is formed to exceed 50%. Vacuum insulation coating
Even if the rate exceeds 50% of the surface area of the outer box, the hard urethane foam
The flexural modulus of the dome is in the range of 8.5-10.0 MPa.
Therefore, there is no problem with the box strength and the weight of the stored items
There is no problem such as the box body not being able to withstand the distortion due to deformation.
In addition, the density of rigid urethane foam is increased due to increased rigidity.
, But the density is in the range of 45-55 kg / m3
Therefore, the heat insulation performance due to the increase of solid heat conduction
There is no decrease in Therefore, even if a large amount of vacuum insulation is used
There is no problem with the quality of the insulation box, and the excellent insulation performance
Energy can be saved.

The heat insulation box according to claim 3 of the present invention has a flexural modulus of 8.0 MPa or more and a density of 60 kg /
It is made of a rigid urethane foam that secures rigidity strength and heat insulation performance as m ³ or less and a vacuum heat insulating material, and the coverage of the vacuum heat insulating material exceeds 40% of the outer box surface area and has three or more doors. Therefore, even if the coverage of the vacuum heat insulating material exceeds 40% of the surface area of the outer box and the number of doors is 3 or more,
Since the rigid urethane foam has a flexural modulus of 8.0 MPa or more, there is no problem with the box strength, and there is no problem with the box deforming because it cannot withstand the strain due to the weight of the stored items. Especially when the number of doors that require rigidity is 3 or more,
There is no deformation. It should be noted that although the density of the rigid urethane foam is increased to increase the strength, since the density is 60 kg / m ³ or less, the heat insulation performance is not deteriorated due to the increase in solid heat conduction. Therefore, even if a large amount of vacuum heat insulating material is used, there is no problem in the quality of the heat insulating box body, and energy saving can be realized by excellent heat insulating performance.

A heat insulating box according to claim 4 of the present invention is a curved box.
Elastic modulus is 8.5 to 10.0 MPa, and density is 45
~ 55kg / m3 rigid urethane foam and vacuum insulation
And the coverage of the vacuum insulation material is 4 of the outer box surface area.
It is more than 0% and has three or more doors.
Therefore, the coverage of the vacuum insulation material exceeds 40% of the outer box surface area,
And even if the number of doors is 3 or more, the hard urethane foam
Bending elastic modulus has a range of 8.5 to 10.0 MPa
Therefore, there is no problem with the box strength, and distortion due to the weight of the stored items
There is no problem such as the box body being unable to withstand and being deformed. Especially rigid
Even if the number of doors that require flexibility is 3 or more, there is no deformation.
Yes. In addition, in order to increase the strength
The density is in the range of 45-55 kg / m3
Since it is, the heat insulation due to the increase of solid heat conduction
There is no decline in Noh. Therefore, use a large amount of vacuum insulation
There is no problem with the quality of the insulation box, and the excellent insulation performance
Therefore, energy saving can be realized.

Further, in the heat insulation box according to claim 5 of the present invention, the rigid urethane foam comprises an isocyanate component composed of a tolylene diisocyanate composition and a premix component composed of a polyol, a foam stabilizer, a catalyst and a foaming agent. Since it is characterized by being obtained by a mixed reaction, a resin having a high elastic modulus can be obtained by using tolylene diisocyanate in which reactive groups are close to each other via an aromatic ring. Therefore, it is not necessary to increase the density extremely, the solid heat conduction is not adversely affected, and excellent heat insulation performance can be maintained. Therefore,
Even a heat-insulating box body having a vacuum heat-insulating material covering more than 50% of the surface area of the outer box can exhibit both strength and high heat-insulating performance.

Further, even in the case of a heat-insulating box having a coverage of the vacuum heat-insulating material exceeding 40% of the surface area of the outer box and having three or more doors, strength and high heat-insulating performance can be exhibited together. .

In the heat-insulating box according to claim 6 of the present invention, since the foaming agent of the rigid urethane foam constituting the water-containing box is made of water, when it is used for foaming by generating carbon dioxide gas by the reaction with isocyanate. At the same time, since the molecular weight is small, a strong reaction bond is formed in the resin molecular structure. Therefore, it is not necessary to increase the density extremely, the solid heat conduction is not adversely affected by the density increase, and excellent heat insulation performance can be maintained. Therefore, even a heat-insulating box body having a vacuum heat-insulating material covering more than 50% of the surface area of the outer box can exhibit both strength and high heat-insulating performance.

Further, since the gas released from the rigid urethane foam at the time of disposal is only carbon dioxide gas, it has an advantage that it can be handled safely even if it is crushed.

Further, even a heat-insulating box having a coverage of the vacuum heat-insulating material exceeding 40% of the surface area of the outer box and having three or more doors can exhibit both strength and high heat-insulating performance. is there.

Further, since the gas released from the rigid urethane foam at the time of disposal is only carbon dioxide gas, it has an advantage that it can be safely handled even if it is crushed.

Further, in the method for producing a raw material according to claim 7 of the present invention, a crushing step of crushing the heat-insulating box according to any one of claims 1 to 6 and a crushing step by this crushing step Waste pieces are put in, and a sorting process is performed to sort into iron, non-ferrous metal and resin dust, and a hard urethane foam block separated from the waste in the crushing process is pulverized by grinding, compression, etc. Foam insulation material treatment step, and liquefied the hard urethane foam powder obtained in the foam insulation material treatment step by an aminolysis reaction operation or a glycolysis reaction operation, etc., and removed resin fine particles and finely ground metal particles as impurities as a filter. After that, it is composed of a raw material manufacturing process in which a raw urethane compound of a rigid urethane foam and a plurality of amines are decomposed by a chemical treatment operation by reaction with supercritical water or subcritical water. The raw material group produced by the waste treatment method is fractionally distilled in the raw material production step, and tolylenediisocyanate composition or tolylenediamine-based polyether polyol is synthesized from tolylenediamine which is one of the fractional components. Therefore, the rigid urethane foam made from the tolylene diisocyanate composition used as the heat insulating material can be industrially recycled again as the raw material for the rigid urethane foam.

Particularly, a crude material group obtained by treatment with supercritical water or subcritical water is fractionally distilled, and tolylenediisocyanate composition and tolylenediamine-based polyether synthesized from tolylenediamine which is one of the fractional components. A polyol is obtained, and it can be easily synthesized as a raw material for producing a rigid urethane foam and recycled.

The heat-insulating box according to claim 8 of the present invention comprises the tolylene diisocyanate composition and tolylene diamine-based polyether polyol polyether polyol obtained in claim 7 as the main raw materials, and is prepared as an auxiliary agent. Foaming agent, catalyst,
Mixing a foaming agent, etc., and injecting it between the inner and outer boxes, and foaming and hardening to make a hard urethane foam, it is obtained by decomposing and synthesizing a tolylene diisocyanate composition as a raw material from a hard urethane foam. By reusing the raw material for the rigid urethane foam, it is possible to obtain a heat-insulating box that enables resource saving.

On the other hand, the refrigerator according to claim 9 of the present invention comprises:
The raw material type of rigid urethane foam is displayed, and the raw material type of the rigid urethane foam used in the waste refrigerator can be determined, and the compatible processing method and raw material manufacturing method can be selected and determined, thereby promoting recycling. It can be done easily.

Further, since the refrigerator according to claim 10 of the present invention records the raw material type of the rigid urethane foam, the recorded information is read at the time of waste treatment of the refrigerator to treat the rigid urethane foam. I can decide.

Further, in the heat insulation box body according to claim 11 of the present invention, the coverage is more than 50% of the outer box surface area and the vacuum heat insulation material having 80% or less, and the bending elastic modulus of 8.0 MPa or more.
Rigidity and heat insulation performance with a density of 60 kg / m3 or less
In a heat-insulating box made of a rigid urethane foam that secures , the vacuum heat-insulating material is composed of a core material and a gas barrier film covering the core material, and the core material is composed of a plurality of sheet-like inorganic fiber aggregates. The heat insulating load of the heat insulating box is effective when the vacuum heat insulating material is arranged from the place where the passing heat gradient inside and outside the box is large and the coverage exceeds about 50% of the surface area of the outer box. The energy saving effect can be enhanced.

By keeping the coverage rate at 80% or less, the effect of using a large amount of the vacuum heat insulating material is not saturated, and the heat absorption load amount is effective when the vacuum heat insulating material has a high utility value. The energy saving effect can be enhanced. For this reason, the initial cost of the product due to the use of this heat-insulating box does not significantly reduce the investment effect due to the use of non-standard vacuum heat-insulating materials and the work of placing them in areas with poor work efficiency. It is possible to prevent an imbalance between an increase and a reduction in running cost due to energy saving.

Further, by using the inorganic fiber as the core material, generation of gas with time in the vacuum heat insulating material is small and the heat insulating performance can be maintained for a long time. In addition, when manufacturing the vacuum heat insulating material, the step of first filling the inner bag with the powder as in the case of using the powder as the core material is omitted, which improves the production efficiency and the working environment.

Further, since the sheet-shaped core material is used, it can be easily used by adjusting it to a required thickness by forming two or more layers, and while ensuring the flow thickness of the rigid urethane foam, the multilayer insulation wall It is possible to effectively enhance the heat insulating property of.

Further, since it is in the form of a sheet, it has high flatness and good adhesion to the outer box, so that the foaming agent at the time of foaming the rigid urethane foam aggregates in the gap between the vacuum heat insulating material and the outer box, and the ambient temperature It is possible to suppress deformation of the surface of the outer box due to expansion and contraction due to changes.

A heat insulating box according to claim 12 of the present invention
Is more than 50% of the surface area of the outer box and 80% or less
A vacuum heat insulating material and flexural modulus of 8.5 to 10.0 MPa
And a urethane foam with a density of 45 to 55 kg / m3
And a vacuum insulation material,
It consists of a core material and a gas barrier film covering the core material.
The core material is composed of a plurality of sheet-like inorganic fiber aggregates.
The vacuum heat insulating material has a large thermal gradient inside and outside the box.
It is installed from the threshold point and the coverage is about 50% of the outer box surface area.
%, The heat absorption load of the insulation box will be effective.
Can be suppressed to
it can.

The coverage should be kept below 80%.
By using a large amount of vacuum insulation,
Effect is not saturated and the value of vacuum insulation is high
Saves energy by effectively reducing the heat absorption load
The effect can be enhanced. For this reason, non-standard forms
Use of vacuum insulation materials and installation work in areas where work efficiency is poor
Without being forced to significantly reduce the investment effect, this disconnection
Increased product initial cost by applying heat box
In addition to the reduction of running cost by energy saving
It can prevent an imbalance.

Further , by using an inorganic fiber as a core material, the vacuum break can be prevented.
Long-term insulation performance with less gas generation in the heat material over time
Can be maintained for a period. In addition, when manufacturing the vacuum insulation material, the powder core
First, enclose the powder in the inner bag as when using it as a material.
The process is also omitted, which improves production efficiency and work environment.
It

Whether the sheet-shaped core material is used
It can be used by adjusting the required thickness with two or more layers.
Easy to do and secure the flow thickness of rigid urethane foam
While effectively increasing the heat insulation of the multi-layer insulation wall
It

Further , since it is in the form of a sheet, it has high flatness and
Due to the good adhesion with the box, there is a gap between the vacuum insulation and the outer box.
When the rigid urethane foam is foamed,
Deformation occurs on the surface of the outer box due to expansion and contraction due to changes in boundary temperature
Can be suppressed.

The heat insulating box according to claim 13 of the present invention is the heat insulating box according to claim 11 or 12 , wherein vacuum heat insulating materials are arranged on both sides, the top, the back, the bottom and the front. Since the vacuum heat insulating material is arranged on all of the six surfaces that are the basic constituent surfaces of the heat insulating box, the vacuum heat insulating material is applied to the six projected surfaces in the heat insulating box, thereby effectively covering the heat insulating box. The energy saving effect can be enhanced by setting the rate to a range of more than 50% and 80% or less of the surface area of the outer box.

A heat insulating box according to a fourteenth aspect of the present invention is the heat insulating wall body according to any one of the eleventh to thirteenth aspects, except for a door formed of hard urethane foam and a vacuum heat insulating material. 20 mm to 50 mm, and the thickness of the rigid urethane foam can be designed to be within a range that can maintain fluidity. Due to deterioration of urethane fluidity, deterioration of insulation performance due to roughness of urethane foam and poor filling. Will not cause. For this reason, the heat insulating effect as a multilayer heat insulating wall with the vacuum heat insulating material is not diminished, and the energy saving effect by applying the vacuum heat insulating material can be sufficiently exerted.

Further, by making the thickness of the heat insulating wall excluding the door not to exceed 50 mm, the application of the vacuum heat insulating material can be utilized for the effect of enhancing the volumetric efficiency of the inner volume with respect to the outer volume of the heat insulating box, and the vacuum The utility value of the heat insulating material can be further increased.

A heat insulation box body according to a fifteenth aspect of the present invention is the hard urethane foam according to any one of the eleventh to thirteenth aspects, wherein the temperature inside the heat insulation box body is a refrigeration temperature. The thickness of the heat insulating wall is 20 mm to 50 mm except for the door formed by the vacuum heat insulating material, and the thickness of the hard urethane foam filled can be designed to be within the range capable of maintaining fluidity. The decrease in fluidity does not cause deterioration of the heat insulation performance due to the roughness of urethane foam or the poor filling. Therefore, the heat insulating effect as a multi-layer heat insulating wall with the vacuum heat insulating material in the freezing temperature region is not diminished, and the energy saving effect can be effectively exhibited in the freezing temperature region where the temperature gradient inside and outside the heat insulating box is large. it can.

Further, by making the heat insulating wall thickness in the freezing temperature region excluding the door not to exceed 50 mm, the application of the vacuum heat insulating material can be utilized for the effect of increasing the volume of the heat insulating box in the freezing temperature region. , The utility value of vacuum insulation can be further increased.

A heat insulation box body according to a sixteenth aspect of the present invention is the hard urethane foam according to any one of the eleventh to thirteenth aspects, wherein the temperature inside the heat insulation box body is a refrigeration temperature. The thickness of the heat insulating wall is 20 mm to 40 mm except for the door formed by the vacuum heat insulating material, and the thickness of the hard urethane foam filled can be designed to be within the range capable of maintaining fluidity. The decrease in fluidity does not cause deterioration of the heat insulation performance due to the roughness of urethane foam or the poor filling. Therefore, the heat insulating effect as a multi-layer heat insulating wall with the vacuum heat insulating material in the refrigerating temperature region is not diminished, and the energy saving by applying the vacuum heat insulating material is achieved in the refrigerating temperature region where the temperature gradient inside and outside the heat insulating box is relatively small. It is possible to realize a heat-insulating box body that balances the effects of improvement in internal volume efficiency inside and outside the heat-insulating box body.

The heat insulation box body according to claim 17 of the present invention is the heat insulation box body according to any one of claims 14 to 16 , wherein the vacuum heat insulating material has a thickness of 10 mm to 20 mm. Since the filling thickness of the rigid urethane foam can be secured within a range where fluidity can be maintained even in a relatively thin portion of 20 to 30 mm, the area where the vacuum heat insulating material can be arranged is widened without impairing the heat insulating property of the multi-layer heat insulating wall, and the coating is performed. The rate can be increased and energy saving effect can be exhibited.

The heat insulating box according to claim 18 of the present invention is the heat insulating box according to any one of claims 11 to 17 , wherein the rigid urethane foam has a thermal conductivity of 0.015 W /
The thermal conductivity of the vacuum heat insulating material in mK is 0.0010
W / mK to 0.0030 W / mK, 1/15 to 1
The ratio of / 5 is set, and in the case where the thickness of the multi-layer heat insulating wall of the rigid urethane foam and the vacuum heat insulating material is thin, the thickness of the vacuum heat insulating material is set to ensure a thickness that does not impair the fluidity of the hard urethane foam. Even if it is thin, the heat insulation performance as a multi-layer heat insulation wall can be maintained, and in order to achieve a high coverage rate, it is possible to save energy in response to the requirement to place a vacuum heat insulating material even in a relatively thin wall of the heat insulation box. The effect can be achieved as expected.

The heat insulating box according to claim 19 of the present invention is the heat insulating box according to any one of claims 11 to 13, wherein a vacuum heat insulating material is embedded in a rigid urethane foam between the outer box and the inner box. Since the entire outer surface of the vacuum insulation material is in close contact with the rigid urethane foam, the insulation box body is separated by peeling compared to the case where the vacuum insulation material is directly contacted with the outer or inner box of the insulation box body. There is no decrease in strength.

Further, as compared with the case where the vacuum heat insulating material is attached to the outer box, the projected area of heat passage between the outer side and the inner side of the heat insulating box can be covered more effectively on the inner side, and even if the used area is the same, it is substantially effective. It is possible to increase the effective coverage.

A heat insulating box according to a twentieth aspect of the present invention is the invention according to any one of the eleventh to thirteenth aspects, wherein a vacuum heat insulating material is provided on a side surface of the heat insulating box between the outer box and the inner box. Tomo When you place is embedded in rigid polyurethane foam
In the case where the vacuum insulation material is installed on the door, the back surface, and the bottom surface,
Is installed in the outer box.Since the side of the outer box and the vacuum heat insulating material do not come into direct contact with each other, the foaming agent of hard urethane foam aggregates in the gap between the outer box and the vacuum heat insulating material, and the environmental temperature changes. Does not expand or contract to deform the outer box.
Therefore, it is possible to prevent the appearance and appearance of the side surface of the heat-insulating box body, which is conspicuous from the outside, from being deteriorated and the quality and value from being deteriorated.

A refrigerator according to claim 21 of the present invention cools the heat insulating box according to any one of claims 11 to 20, a cooling chamber formed in the heat insulating box, and the cooling chamber. It is composed of a cooling device, and by reasonably realizing a heat-insulating box body with a high coverage of the vacuum heat-insulating material with respect to the surface area of the outer box, in addition to high energy-saving effect, high internal volume efficiency and We can provide environment-friendly refrigerators with excellent basic functions that meet space requirements.

Embodiments of a heat insulating box, a raw material manufacturing method, and a refrigerator according to the present invention will be described below with reference to FIGS.
Will be explained.

(Embodiment 1) FIG. 1 shows a heat insulating box body according to an embodiment of the present invention. Reference numeral 1 denotes a heat insulating box, in which a hard urethane foam 5 and a vacuum heat insulating material 6 are arranged in a multi-layer structure in a space 4 formed by an inner box 2 made of synthetic resin and an outer box 3 made of metal.
In manufacturing the heat insulating box body 1, the vacuum heat insulating material 6 is bonded and fixed to the outer box 3 in advance, and the raw material of the hard urethane foam 5 is injected to perform integral foaming. The vacuum heat insulating material 6 is
It is arranged so as to occupy 80% of the surface area of the outer box 2.

The raw material for the rigid urethane foam is 100 parts by weight of a polyether having a hydroxyl value of 380 mgKOH / g, 3 parts by weight of a catalyst, 3 parts by weight of a foam stabilizer, 2 parts by weight of a foaming agent consisting of water, and a reaction modifier as other components. 0.5 formic acid
A premix prepared by adding and mixing parts by weight is prepared in advance, and then mechanically mixed with an isocyanate composed of a tolylene diisocyanate composition to form a rigid urethane foam 5.

At this time, the density of the rigid urethane foam on the side surface of the heat insulating box 1 which greatly affects the strength of the casing is 45 k.
The flexural modulus was 8.5 MPa at g / m ³ . The thermal conductivity of the rigid urethane foam at this time is 0.022.
It was W / mK. This physical property has a density of 1.3 times and a flexural modulus of 1.
The thermal conductivity was 5 times, and the thermal conductivity was almost the same.

When the density is increased to 55 kg / m ³ , the flexural modulus is 10.0 MPa and the thermal conductivity is 0.0
23 W / mK, and when the density was further increased to 70 kg / m ³ , the flexural modulus was 13.0 MPa, the thermal conductivity was 0.026 W / mK, and the heat insulation performance was significantly deteriorated (shown in Table 1). .

[0122]

[Table 1]

The above corresponds to claims 1 to 4 described in the claims of the present application.

After that, a refrigerator (not shown) is completed by incorporating components such as a storage rack (not shown) and a cooling system (not shown) in the heat insulating box 1, but the box is distorted by the cooling test. It was found that the quality of the box body was ensured without any deformation or gap between the door and the flange even in the repeated loading / unloading test when the food was stored in the storage rack or the storage rack. . Therefore, in order to secure the heat insulating performance and the rigidity strength as the heat insulating box, it was found that the density is 60 kg / m ³ or less and the flexural modulus is 8.0 MPa or more.

(Embodiment 2) FIG. 2 is a process chart showing a raw material manufacturing method in Embodiment 2, and corresponds to claim 5 in the claims of the present application.

First, the outline of the waste treatment procedure will be described.

The transported heat insulating box 1 of the refrigerator first passes through the crushing step 7 and proceeds to the sorting processing step 8. In the sorting process 8, the waste crushed in the crushing process 7 is divided into heavy waste and light waste, and each predetermined material is separated and collected. Here, in the foam insulation material treatment step 9 in the light waste sorting process, the rigid urethane foam 5 and the foam gas contained in the refrigerator are collected. Next, the discharged rigid urethane foam 5 proceeds to the raw material production step 10.
It is decomposed into raw material compounds and amines of rigid urethane foam.

Next, the processing procedure will be described in detail with reference to FIG.

In FIG. 2, the waste of the heat insulating box 1 conveyed to the waste treatment facility is put into the crushing process 7 in step 21. In the case of a refrigerator, the refrigerant in the refrigerator should be drained before adding the ingredients. Then, the waste in which the material has been charged is transferred to the preshredder by the conveyor (step 22).

The waste crushed by the preshredder in the coarse crushing in step 23 is put into a crusher. In step 24, the waste shredded in the previous step is further finely crushed by a uniaxial car shredder having an output of about 1000 horsepower.

In step 25, the vibrating conveyor disposed below the take-out part of the car shredder separates heavy iron, non-ferrous metal, and light wastes other than rubbers, and in step 26, it is transferred by a belt type conveyor. .

Magnetic force sorter of step 27, step 28
The waste is separated into those containing iron-based metal and those not containing iron-based metal by the vibrating conveyor in step No. 2 and the magnetic separation drum in step 29.

At step 27A, the lightweight dust that floats up at step 26 and step 27 is collected and transferred to the dust collecting step (not shown) through the duct.

The waste separated in step 29 is transferred by a conveyor (step 30), and is manually sorted on this conveyor into iron and other parts (step 31). The iron selected by the manual selection in step 31 is transferred by a conveyor to a cart for integrated transportation (step 32), and wastes other than iron such as motor scraps and cables are separated by manual selection.

The waste material containing no ferrous metal separated in step 29 is transferred to the conveyor (steps 52 and 54) while the non-ferrous metal is manually selected (step 53) and left. Waste including dust such as rubber is separated and accumulated.

As described above, the crushing step 1 described in the claims of the present application is performed by each means and steps from step 21 to step 24, and the sorting processing step 2 is performed from step 25 to step 32. , And step 52
These correspond to the respective means and steps from to step 54.

Next, the hard urethane foam 5 separated in the crushing step is sucked into the cyclone in the foam insulation processing step 9 through the duct (step 33). In this cyclone, a relatively large lump of hard urethane foam 5 is separated and collected (step 35). The blowing agent gas in the rigid urethane foam collides with the cyclone bag filter together with the small pieces of rigid urethane foam (step 3).
6) Then, the foaming agent gas passes and is sent to the recovery device and recovered (step 37). If the blowing agent gas is carbon dioxide, it is not collected. In the case of cyclopentane, it is a recovery device for the explosion-proof system.

The lumps and small pieces of the hard urethane foam 5 separated by the cyclone (step 35) and the bag filter (step 36) are sent to the foam volume reducing machine (step 41). Foam volume reduction machine (step 41)
Is composed of a press or a screw type compressor, and grinds and pulverizes the lumps and small pieces of the rigid urethane foam 5 by the shearing force at the time of compression to reduce the volume. During compression grinding, the blowing agent gas dissolved in the rigid urethane foam can be vaporized by heating and efficiently recovered.

As described above, the foam insulation material treatment step 9 described in the claims of the present application corresponds to each means and step from step 33 to step 41.

Next, the rigid urethane foam 5 pulverized in the foam insulation treatment step 9 is sent to a reaction tank and subjected to a glycolysis reaction operation by mixing and heating with ethylene glycol, monoethanolamine, tolylenediamine and the like. A liquefied substance is produced by the or aminolysis reaction operation (step 42).

After this, filter filtration (step 4
In 3), the impurity solid particles are removed, introduced into the reactor together with high-temperature high-pressure water, and maintained in a supercritical or subcritical state to cause a decomposition reaction (step 44).

The discharged liquid after the decomposition reaction is subjected to removal of water, carbon dioxide and the like in a dehydration tower (step 45), and then a raw material compound of the rigid urethane foam 5 and amines are obtained.

As described above, the remanufacturing process 10 described in the claims of the present application corresponds to each means and process from step 42 to step 45.

Thereafter, in the raw material production step 11, the decomposition product is fractionally distilled (step 46), and one of the components obtained by fractional distillation is converted from tolylenediamine to a tolylenediisocyanate composition or tolylenediamine-based polyamine. Raw materials are manufactured by synthesizing into ether polyol (step 47).
A, 47B).

(Embodiment 3) A heat insulating box according to an example of Embodiment 3 will be described with reference to FIG.

The raw material for the rigid urethane foam is 100 parts by weight of the tolylenediamine-based polyether polyol having a hydroxyl value of 380 mgKOH / g, which uses the tolylenediamine obtained in Embodiment 2 as a starting material, 3 parts by weight of a catalyst, and a foam stabilizer. 3 parts by weight of the agent, 2 parts by weight of a foaming agent consisting of water, and 0.5 parts by weight of formic acid as a reaction modifier as other components are added and mixed in advance to prepare a premix. Mechanical mixing with an isocyanate composed of the tolylene diisocyanate composition obtained in 2 produces a rigid urethane foam 5.

As described in the first embodiment, the inner box 2 and the outer box 3 to which the vacuum heat insulating material is adhered and fixed in advance are formed, and the rigid urethane foam 5 is injected and filled along the formed heat insulating wall 4. A heat insulation box is obtained.

(Fourth Embodiment) FIG. 3 shows a refrigerator according to an embodiment of the fourth embodiment.
Reference numeral 12 is a refrigerator, which is made of hard urethane foam 5 as a heat insulating material. Reference numeral 3 is a display management plate attached to the refrigerator, and specifies the raw material type of the rigid urethane foam 5.

Further, the display management board 13 may be a smart media, a bar code or the like recorded thereon. In this case,
When crushing a refrigerator, this information can be read to select a treatment method for rigid urethane foam.

(Fifth Embodiment) A heat insulating box and a refrigerator equipped with the heat insulating box according to the fifth embodiment will be described with reference to FIGS. 4 to 6.

In FIG. 4 and FIG. 5, 101 is a refrigerator main body, 102 is a heat insulating box body including a door 103, and is formed from an inner box 104 made of synthetic resin and an outer box 105 made of metal such as iron plate. A hard urethane foam 107 and a vacuum heat insulating material 108 are arranged in a multi-layered structure in a space 106. In manufacturing the heat insulating box 102, the vacuum heat insulating material 108 is bonded and fixed to the outer box 105 in advance, and the raw material of the hard urethane foam 107 is injected to perform integral foaming.

The vacuum heat insulating material 108 is evenly arranged on both side surfaces, the top surface, the back surface, the bottom surface of the heat insulating box 102, and each surface of the door 103, and occupies 80% of the surface area of the outer box 105. Has been done.

109 is a freezer, 110 is a refrigerator, and 111
Is a vegetable compartment and constitutes a cooling compartment. Freezer 109
Is in the freezing area of approximately -15 ° C to -25 ° C in the refrigerating chamber 11
0, the vegetable compartment 111 is set to a refrigerating region of approximately 0 to 10 ° C. 112 is a compressor, 113 is condenser 114,115
Is a cooler and constitutes a cooling device.

The refrigerator main body 101 is provided with a heat insulating box 102, a freezing compartment 109, a refrigerating compartment 110, a vegetable compartment 111, and a compressor 112, a condenser 113, and coolers 114 and 115 for cooling these cooling compartments. It is composed of devices.

Further, in FIG. 6, the vacuum heat insulating material 108 is used.
Is formed by heating and drying the inorganic fiber aggregate 116 such as glass wool, inserting it into the outer covering material 117, and drawing a vacuum inside to seal the opening.

The fiber diameter of the inorganic fiber aggregate 116 is 0.1 μm.
Vacuum heat insulating material 10 is used in the range of m to 1.0 μm.
When the thermal conductivity of No. 8 is 0.015 W / mK when the thermal conductivity of the rigid urethane foam 107 is 0.001 W / mK, the thermal conductivity of 1/10 is set to 0.0015 W / mK. Applied.

The outer cover material 117 has a laminated film made of polyethylene terephthalate (12 μm) as a surface protective layer on one side, an aluminum foil (6 μm) as an intermediate portion, and a high-density polyethylene (50 μm) heat seal layer on the other side. On the surface of, the surface protective layer was polyethylene terephthalate (12 μm), the middle part was a film layer obtained by aluminum vapor deposition on the inside of the ethylene-vinyl alcohol copolymer resin composition (15 μm), and the heat seal layer was a high density polyethylene ( It is a laminated film composed of 50 μm).

Further, the outer cover material 117 is formed with a nylon resin layer as a surface protective layer in order to improve scratch resistance.

The heat insulating wall thickness of the heat insulating box body 102 is equal to that of the door 103.
Except for the thin wall portion of the opening, the freezer compartment 109
In the freezing area of 25 to 50 mm, the refrigerator compartment 1
10, 25-40 mm in the cold storage area of the vegetable compartment 111
The vacuum heat insulating material 108 having a thickness of 15 mm is disposed in this heat insulating wall, and the rigid urethane foam 1
Care is taken to secure a thickness of at least 10 mm filled with 07.

With the above structure, the vacuum heat insulating material 1
When a large amount of 08 is arranged and the coverage is to be increased to the limit, parts (not shown) of the refrigerator main body 101 or parts having a special structure (uneven shape, piping, installation part of drain pipe, etc.)
Then you need a special form of vacuum insulation 108,
The workability of attaching the vacuum heat insulating material 108 becomes very poor.

In consideration of the heat transmission projection surface to the inside of the refrigerator such as the corners of the heat insulating box 102 and the heat insulating partition between the freezer compartment 109 and the vegetable compartment 111, the vacuum heat insulating material 108 is extended to the end. However, there are some areas where it is almost impossible to expect additional insulation.

Therefore, the surface area of the outer box 105 is approximately 80
%, Even if the vacuum heat insulating material 108 is to be arranged, the above-mentioned use efficiency is poor and the utility value is saturated, so that the effect of improving the heat insulating performance against the injection of the vacuum heat insulating material 108 is significantly reduced. .

Therefore, as in the present embodiment, the coverage of the vacuum heat insulating material 108 with respect to the surface area of the outer box 105 is 8%.
By keeping the content at 0%, the effect of using a large amount of the vacuum heat insulating material 108 is not saturated, and the heat absorption load amount can be effectively suppressed in a state of high utility value, and the energy saving effect can be enhanced. it can.

Further, the coverage of 80% is obtained on both side surfaces, top surface, back surface, bottom surface, and front surface of the heat insulating box 102, that is, the door 1.
By arranging a large-sized vacuum heat insulating material 108 that can substantially cover each surface of 03, the workability of attachment can also be realized.

Therefore, the vacuum heat insulating material 10 having a nonstandard form is used.
This heat-insulating box body 1 does not have a significant decrease in the investment effect due to the use of 8 and the work of arranging it in a portion with poor work efficiency.
By applying 02, the balance between the increase in the initial cost of the refrigerator body 1 and the reduction in the running cost due to the energy saving is not lost, and the value as the life cycle cost can be increased.

In addition, in this embodiment, the vacuum heat insulating material 108 is used.
Although the coverage of the outer box 105 to the surface area of the outer box is 80%, since the heat insulating wall thickness wraps around the periphery of each surface of about 50 mm and the partition between cooling chambers, it does not become a projection surface to the inside of the cabinet. Consider arranging it avoiding parts,
Considering the filling adhesion of the hard urethane foam 107 around the periphery of the opening, and taking into account that the position where the vacuum heat insulating material 108 is arranged is slightly rearward, etc., there are some restrictions such as workability of sticking, but the coverage is generally. Even at about 75%, it is possible to maintain almost the same heat insulation effect. In this embodiment, the heat insulating box 1
The outer dimensions of 02 were 1800 mm in height, 675 mm in width, and 650 mm in depth.

Further, the heat absorption load amount of the heat insulating box is effective if the heat insulating load is arranged from the inside and outside of the heat insulating box 102 where the passing heat gradient is large and the coverage exceeds about 50% of the surface area of the outer box 105. The energy saving effect can be enhanced.

The temperature gradient inside and outside the compartment of the door 103 is related to the exhaust heat of the compressor 112 and the condenser 113.
Since it is relatively smaller than the other parts, and the strength against the stored items inside the cabinet supported by the door 103 and the mechanical peeling of the vacuum heat insulating material 108 due to the opening and closing of the door are required, the vacuum heat insulation to the door 103 is intentionally performed. It is conceivable to refrain from disposing the material 108 and efficiently obtain the effect of applying the vacuum heat insulating material 108 to the other main body portion of the heat insulating box 102. At this time, the coverage of the vacuum heat insulating material 108 is about 53%.

Further, the heat insulating wall of the heat insulating box 102 formed of the hard urethane foam 107 and the vacuum heat insulating material 108 which surrounds the freezing chamber 109 in the freezing area is the thin wall portion of the opening except the door 103. Including the door 103, the heat insulating wall thickness of the heat insulating box body 102 formed by the hard urethane foam 107 and the vacuum heat insulating material 108 that surround the refrigerating compartment 110 and the vegetable compartment 111 in the refrigerating region in a distribution of 25 to 50 mm is the same as the opening. The distribution is 25 to 40 mm including the thin wall portion of the portion, and the vacuum heat insulating material 108 having a thickness of 15 mm is arranged in this heat insulating wall thickness.
The thickness of 7 to be filled is at least 10 mm. For this reason, the flowability of the rigid urethane foam 107 during foaming is not hindered, and the heat insulation is not deteriorated due to the roughness of the foam or defective filling.

As described above, the thickness of the vacuum heat insulating material 108 is ensured and the heat insulating property is sufficiently exhibited, while the heat insulating property of the rigid urethane foam 107 is also maintained to effectively enhance the heat insulating performance as the multi-layer heat insulating wall. You can In particular, it is more effective in the freezing temperature region where the temperature gradient inside and outside the refrigerator is large.

Then, the heat insulation wall thickness of the freezer compartment 109 is set to 50 m.
By not exceeding m, the application of the vacuum heat insulating material 108 can be utilized to increase the internal volume of the freezing compartment 109 having a relatively small volume ratio without affecting the external layout. The utility value of can be increased.

Further, by making the heat insulating wall thickness of the refrigerating compartment 110 and the vegetable compartment 111 not to exceed 40 mm, energy saving can be achieved by applying the vacuum heat insulating material 108 in the refrigerating temperature region where the temperature gradient inside and outside the refrigerator is relatively small. And insulation box 10
2 The effect of improving the internal volume efficiency inside and outside can be balanced.

If the contribution to the inner volume of the vacuum heat insulating material 108 is diverted to the compact outer volume while keeping the inner volume stationary, it is possible to save the installation space of the refrigerator main body 101.

It is to be noted that the thickness of the heat insulating wall of the door 103 is not intentionally defined within these ranges because the strength of the door 103 for supporting the stored items in the refrigerator and the recessed portions of the handle, the operation portion of the function, the display portion, etc. This is because there are cases where existence should be considered.

The vacuum heat insulating material 108 has a thickness of 10 mm.
To a certain extent, the influence of so-called heat bridge through the outer skin material 117 is not relatively large and the heat insulation performance of a single item can be generally maintained. Therefore, even if the wall thickness of the multi-layer heat insulation wall is set to a minimum of 20 mm, the thickness of the rigid urethane foam 107 can be reduced. 10 mm can be secured, and the desired heat insulating effect can be obtained.

On the other hand, the thickness of the vacuum heat insulating material 108 can be increased to further enhance the heat insulating effect.
If it exceeds, the effect of improving the heat insulation on the same surface will be saturated, and it is more rational to divide the thickness and spread it on other surfaces. Therefore, the thickness of the vacuum heat insulating material 108 is 10 mm.
-20 mm is suitable.

The vacuum heat insulating material 108 uses the inorganic fiber aggregate 116 as the core material and has a fiber diameter of 0.1 μm to 1.0 μm.
Since it is used in the range of μm, vacuum heat insulating material 10
When the thermal conductivity of the rigid urethane foam 107 is 0.015 W / mK, the thermal conductivity of No. 8 is 0.0015 W / mK, which is 1/10 by the same measurement standard. For this reason, if the coverage is increased to nearly 80%, the heat insulation performance becomes extremely high and a large energy saving effect is obtained. Further, since the inorganic fiber aggregate 116 is used, gas generation in the vacuum heat insulating material 108 over time is small, and when the vacuum heat insulating material 108 is manufactured, the inner bag is first powdered so that the powder is used as the core material. The process of enclosing the body is also omitted, improving production efficiency and working environment.

Therefore, the vacuum heat insulating material 10 is increased in coverage.
Even if a large amount of 8 is used, it is possible to obtain the heat-insulating box 102 having excellent reliability over time and excellent productivity.
The energy saving effect of 1 can be continuously maintained.

In the embodiment of the present invention, the thermal conductivity of the vacuum heat insulating material 108 is 0.015 and the thermal conductivity of the rigid urethane foam is 0.015.
When W / mK was set, 0.0015 and 1/10 were applied, but the inorganic fiber aggregates 116 having different fiber diameters were adopted, and 0.0010 W / mK to 0.0030 W
/ MK may be in the range of the ratio of 1/15 to 1/5.

Within this range, in the case where the thickness of the multi-layered heat insulating wall between the hard urethane foam 107 and the vacuum heat insulating material 108 is thin, the vacuum heat insulating material is provided in order to secure a thickness that does not impair the fluidity of the hard urethane foam 107. Even if the thickness of 108 is reduced, the heat insulation performance as a multi-layer heat insulation wall can be maintained,
In order to realize a high coverage, the energy saving effect can be expected as expected, in response to the request to dispose the vacuum heat insulating material 108 even in a portion where the wall thickness of the heat insulating box 102 is relatively thin.

(Sixth Embodiment) A heat insulating box and a refrigerator provided with this heat insulating box according to the sixth embodiment will be described with reference to FIG. The description of the same configuration as that of the fifth embodiment will be omitted, and only different points will be described.

In FIG. 7, 118 is a sheet-like inorganic fiber aggregate such as glass wool, and these sheet-like inorganic fiber aggregates 118 having a thickness of 5 mm are stacked and enclosed in a gas barrier outer skin material 119, and vacuum degassing is performed. Then vacuum insulation 12
Configures 0.

Since the thin sheet-shaped core material is used, it can be easily used by adjusting it to a required thickness by forming two or more layers. Further, depending on the required shape, there are three layers in some places, five layers in some places, etc. Even in one vacuum heat insulating material, different number of layers can be formed to form a different shape vacuum heat insulating material, and the flow part of the rigid urethane foam 107 can be formed. It is possible to effectively enhance the heat insulating property of the multilayer heat insulating wall while ensuring the thickness.

Further, a bent portion can be formed to form a three-dimensional vacuum heat insulating material 120 conforming to the shape of the heat insulating box, and the coverage of the outer box 105 with respect to the surface area can be reasonably increased.

Further, since it is sheet-shaped and has high flatness and good adhesion to the outer box, the vacuum heat insulating material 120 and the outer box 1 are
It is possible to suppress the occurrence of deformation of the surface of the outer casing 105 due to expansion and contraction of the foaming agent of the rigid urethane foam 107 during foaming due to expansion and contraction due to environmental temperature changes.

As described above, a core material having an infinite number of patterns can be produced very easily with one kind of core material, and since it has a plurality of layers, the exhaust efficiency at the time of vacuum exhaust is also improved, and the productivity is improved.
It also reduces material costs.

An adhesive or the like may be used between the layers to fix each layer, but it is better to use the sheets only one on top of each other in order to suppress gas generation as much as possible or to reduce material costs and man-hours. preferable.

(Embodiment 7) A heat insulating box and a refrigerator equipped with this heat insulating box according to the seventh embodiment will be described with reference to FIGS. 8 and 9. The description of the same configuration as that of the fifth embodiment will be omitted, and only different points will be described.

In FIG. 8 and FIG. 9, the vacuum heat insulating material 121 is arranged in the intermediate layer of the wall thickness of the heat insulating box 122, and the entire circumference is adhered by the hard urethane foam 107. Door 1
03 and only the back surface of the heat insulating box 122 are attached to the outer box 105 by adhesion, as in the fifth embodiment.

With the above structure, the vacuum heat insulating material 1
Since the outer surface of 21 is in close contact with the hard urethane foam 107, the strength of the heat insulating box body 122 does not decrease due to peeling, as compared with the case where the outer box 105 or the inner box 104 directly contacts the vacuum heat insulating material.

Further, as compared with the case where the vacuum heat insulating material 121 is attached to the outer box 105, the heat passage projected area between the outer side and the inner side of the heat insulating box 122 can be covered more effectively inside.
Even if the used area is the same, it is rational because the substantial coverage can be increased.

On the side surface of the heat insulating box 122, the outer box 1
Since the side surface of 05 and the vacuum heat insulating material 121 do not directly contact,
The foaming agent of the hard urethane foam 107 is not aggregated in the gap between the outer case 105 and the vacuum heat insulating material 121, and the outer case 105 is not deformed by expanding and contracting due to a change in environmental temperature.
For this reason, it is possible to prevent deterioration of the quality and value of the refrigerator by spoiling the appearance of the side surface of the heat insulating box 122 that is easily noticeable from the outside.

The vacuum heat insulating material 121 may be arranged on the intermediate layer of the heat insulating wall over the entire area of the heat insulating box 122 if possible, but in the present embodiment, the door 103 and The back and bottom of the heat insulating box 122 are the outer box 105.
It is supposed to be adhered to and arranged. This is the door 10
Regarding No. 3, due to the difference in urethane foaming method, it is difficult for urethane to spread to the surface layer in the intermediate layer arrangement.
Regarding the back surface and the bottom surface of No. 2, in the middle layer arrangement, they interfere with the piping of the cooling device and the drain pipe of the defrosting water of the coolers 114 and 115, and in the manufacturing process, the back plate, the bottom plate and the vacuum heat insulating material 12
This is because it is preferable to assemble 1 as an integrated product.

[0194]

As is apparent from the above description,
Flexural modulus of 8.0 MPa or more and density of 60 kg
/ M ³ or less , and is composed of a rigid urethane foam that secures rigidity strength and heat insulation performance and a vacuum heat insulating material.

The flexural modulus is 8.5 to 10.0MP.
Hard urethane with a and density of 45 to 55 kg / m3
It consists of foam and vacuum insulation.

Further, since the vacuum heat insulating material has a coverage rate of more than 50% of the outer surface area of the outer box, energy saving can be realized by excellent heat insulating performance, and at the same time, there is no problem with the strength of the box and the contents can be stored. There is no problem that the box body is deformed because it cannot withstand the distortion due to the weight.

Further, the same effect can be obtained even in the case of a heat insulating box having a coverage of the vacuum heat insulating material exceeding 40% of the surface area of the outer box and having three or more doors.

Particularly, an isocyanate component in which the rigid urethane foam is a tolylene diisocyanate composition,
Since it is obtained by mixing and reacting a premix component consisting of a polyol, a foam stabilizer, a catalyst, and a foaming agent, the use of tolylene diisocyanate causes the reactive groups to come close to each other via an aromatic ring, resulting in elastic modulus. It is possible to obtain a high resin. For this reason, it is possible to maintain an excellent heat insulating performance without being adversely affected by solid heat conduction without requiring an extreme increase in density.

Furthermore, since the foaming agent of the rigid urethane foam constituting the composition is made of water, carbon dioxide gas is generated by the reaction with isocyanate to be used for foaming, and at the same time, a strong reaction bond is formed due to the small molecular weight of the resin molecule. Form in the structure. Therefore, it is not necessary to increase the density extremely, the solid heat conduction is not adversely affected, and excellent heat insulation performance can be maintained. Therefore, even if the coverage rate of the vacuum insulation material exceeds 50% of the outer surface area of the outer box, or even if it is an insulation box body with a coverage rate of 40% or more and three or more doors, the strength and high heat insulation performance are combined. You can do it.

Further, since the gas released from the rigid urethane foam at the time of disposal is only carbon dioxide gas, it has an advantage that it can be handled safely even if it is crushed.

Further, in the case of a heat insulating box made of a hard urethane foam made from a tolylene diisocyanate composition as a raw material, a crushing step of crushing the heat insulating box and a waste piece crushed by this crushing step are charged, Iron, a non-ferrous metal and a sorting treatment step of sorting into resin dust and the like, a foam insulation material treatment step of grinding the hard urethane foam lump separated from the waste in the crushing step, and pulverizing by compression, etc., The hard urethane foam powder obtained in the foam insulation treatment step is liquefied by an aminolysis reaction operation or a glycolysis reaction operation and the like, and resin fine particles or fine metal pulverized material particles that become impurities are removed by a filter, and then supercritical water or a subcritical water is used. Re-raw material manufacturing process that decomposes into raw material compounds of rigid urethane foam and multiple amines by chemical treatment operation by reaction with critical water The raw material group produced by the waste treatment method consisting of is fractionated in the raw material manufacturing step, and tolylenediisocyanate composition or tolylenediamine-based polyether polyol is synthesized from tolylenediamine, which is one of the fractional components. Since the raw material manufacturing method becomes possible, the rigid urethane foam using the tolylene diisocyanate composition used as a heat insulating material as a raw material can be industrially recycled as a raw material for the rigid urethane foam again. In particular, the raw material group obtained by treatment with supercritical water or subcritical water is fractionally distilled to obtain a tolylene diisocyanate composition or tolylene diamine-based polyether polyol synthesized from tolylene diamine, which is one of the fractional components. It can be easily synthesized as a raw material for the production of rigid urethane foam and recycled.

Further, the obtained tolylene diisocyanate composition or tolylene diamine type polyether polyol polyether polyol is used as a main raw material, and an auxiliary agent is mixed with a foam stabilizer, a catalyst, a foaming agent and the like to prepare an inner box and an outer box. Since the rigid urethane foam that is injected and foamed and cured is used as the heat insulating material, it is possible to manufacture a heat insulating box body that enables resource saving.

On the other hand, since the type of raw material of rigid urethane foam is displayed or recorded in the refrigerator,
Since it is possible to determine the raw material type of the rigid urethane foam used in the heat insulation box of the waste refrigerator, it is possible to select and determine a suitable processing method and raw material manufacturing method, and to easily recycle it.

As described above, according to the present invention, even if a large amount of vacuum heat insulating material is used, there is no problem in the strength of the box body and the heat insulating box body having high heat insulating performance is provided. At the same time, the material of the used heat insulating box body is recycled. The present invention provides a manufacturing method of a raw material and a refrigerator that improve the rate and facilitate recycling.

Further, the vacuum heat insulating material having a coverage of more than 50% and less than 80% of the surface area of the outer box and a flexural modulus of 8.0.
Rigid when the pressure is above MPa and the density is below 60 kg / m3
Is a heat-insulating box body made of a rigid urethane foam that secures heat-resistant strength and heat-insulating performance , wherein the vacuum heat-insulating material is composed of a core material and a gas barrier film covering the core material, and the core material is a sheet of a plurality of layers. It consists of an inorganic fiber aggregate.

[0206] Further , the covering rate exceeds 50% of the outer box surface area.
The vacuum heat insulating material is 80% or less and the flexural modulus is 8.5.
~ 10.0 MPa, and a density of 45-55 kg / m3
A heat-insulating box made of the rigid urethane foam of
The vacuum heat insulating material covers a core material and a gas barrier layer covering the core material.
The core material is a sheet-like inorganic fiber having a plurality of layers.
Since it is made of a fiber aggregate , the heat absorption load amount can be effectively suppressed in a state where the utility value of the vacuum heat insulating material is not saturated and the energy saving effect can be enhanced. Therefore, it is possible to prevent an imbalance between the increase of the initial cost of the product and the reduction of the running cost due to the energy saving by applying the heat insulating box without significantly reducing the investment cost effect.

Further, by using the inorganic fiber as the core material, generation of gas with time in the vacuum heat insulating material is small and the heat insulating performance can be maintained for a long time. In addition, when manufacturing the vacuum heat insulating material, the step of first filling the inner bag with the powder as in the case of using the powder as the core material is omitted, which improves the production efficiency and the working environment.

Further, since the sheet-shaped core material is used, it can be easily used by adjusting the thickness to two layers or more so that the thickness of the rigid urethane foam can be adjusted to the required thickness, and the multilayer insulation wall can be secured. It is possible to effectively enhance the heat insulating property of.

Further, since it is a sheet and has high flatness and good adhesion to the outer box, the foaming agent at the time of foaming the rigid urethane foam aggregates in the gap between the vacuum heat insulating material and the outer box, and the ambient temperature It is possible to suppress deformation of the surface of the outer box due to expansion and contraction due to changes.

Further, the vacuum heat insulating material is provided on both side surfaces, the top surface, the back surface,
Since it is arranged on each of the bottom surface and the front surface, the vacuum heat insulating material is applied to all six projection surfaces in the heat insulating box body, and the coverage is effectively more than 50% of the outer box surface area and 80% or less. The energy saving effect can be enhanced by setting the range.

[0211] Further, the entire thickness of the heat insulating wall except for the door formed of the rigid urethane foam and the vacuum heat insulating material is 20 mm-
Since the thickness is 50 mm, the deterioration of the fluidity of the urethane does not cause the deterioration of the heat insulation performance due to the roughness of the urethane foam or the poor filling. Therefore, the heat insulating effect as a multilayer heat insulating wall together with the vacuum heat insulating material is not impaired, and the energy saving effect can be sufficiently exerted.

Also, by making the thickness of the heat insulating wall excluding the door not to exceed 50 mm, the application of the vacuum heat insulating material has the effect of increasing the volumetric efficiency of the inner volume with respect to the outer volume of the heat insulating box and the same inner volume. It can also be used for space saving by reducing the outer volume, and the utility value of the vacuum heat insulating material can be further enhanced.

[0213] In addition, the entire thickness of the heat insulating wall except for the door formed of the rigid urethane foam and the vacuum heat insulating material in the region where the temperature inside the heat insulating box is maintained at the freezing temperature is 20 mm to 50 mm.
Since it is set to mm, the heat insulating effect as a multi-layer heat insulating wall with the vacuum heat insulating material is not impaired, and the energy saving effect and the internal volume increasing effect can be effectively achieved in the freezing temperature region where the temperature gradient inside and outside the heat insulating box is large. Can be demonstrated.

[0214] Further, all the thickness of the heat insulating wall except for the door formed of the hard urethane foam and the vacuum heat insulating material in the region where the temperature inside the heat insulating box is maintained at the refrigerating temperature is 20 mm to 40 mm.
Since it is set to mm, the heat insulating effect as a multi-layer heat insulating wall with the vacuum heat insulating material is not diminished, and energy saving is achieved by applying the vacuum heat insulating material in the refrigerating temperature region where the temperature gradient inside and outside the heat insulating box is relatively small. It is possible to realize a heat insulating box in which the effects of improving the internal volume efficiency inside and outside the heat insulating box are balanced.

Also, the thickness of the vacuum heat insulating material is 10 mm to 20 mm.
Since the thickness is set to mm, it is possible to secure the filling thickness of the rigid urethane foam within a range in which the fluidity can be maintained even in a relatively thin wall thickness of 20 to 30 mm, and the vacuum heat insulating material is distributed without impairing the heat insulating property of the multi-layer heat insulating wall. The area that can be provided is expanded, the coverage rate can be increased, and the energy saving effect can be exhibited.

Further, since the vacuum heat insulating material is composed of the core material of the inorganic fiber aggregate and the gas barrier film covering the core material, the vacuum heat insulating material has good workability, so that it is easy to increase the coverage of the heat insulating box, and the vacuum insulating material It is possible to obtain a heat-insulating box body that has little time-dependent gas generation in the heat-insulating material and has excellent reliability over time and productivity even when a large amount of vacuum heat-insulating material is used.

Further, when the thermal conductivity of the rigid urethane foam is 0.015 W / mK, the thermal conductivity of the vacuum heat insulating material is 0.0010 W / mK to 0.0030 W / mK, and 1/15 to 1/5. Since the ratio is set, the vacuum heat insulating material can be arranged even in a portion where the wall thickness of the heat insulating box is comparatively thin without lowering the heat insulating property of the hard urethane foam, which realizes a high coverage and an energy saving effect. Can be demonstrated.

Further, since the vacuum heat insulating material is embedded and arranged in the hard urethane foam between the outer box and the inner box, the entire outer surface of the vacuum heat insulating material is in close contact with the hard urethane foam, and the strength of the heat insulating box does not decrease. .

Further, compared with the case where the vacuum heat insulating material is attached to the outer box, the projected area of heat passage between the outer side and the inner side of the heat insulating box can be covered more effectively inside, and even if the use area is the same, it is substantially effective. It is possible to increase the effective coverage.

Also, place the vacuum heat insulating material on the side surface of the heat insulating box.
It is embedded in a rigid urethane foam between the outer box and the inner box, and the vacuum heat insulating material is placed on the door, back, bottom.
Since it is installed in the outer box, the foaming agent of hard urethane foam aggregates in the gap between the outer box and the vacuum heat insulating material, expands and contracts due to changes in environmental temperature, and deforms the outer box for heat insulation. It is possible to prevent the appearance quality of the side surface of the box body from being impaired.

The heat insulating box body according to any one of claims 11 to 20, a cooling chamber formed in the heat insulating box body, and a cooling device for cooling the cooling chamber. It is a refrigerator, and by reasonably realizing a heat-insulating box that has a high coverage of the vacuum heat-insulating material with respect to the surface area of the outer box, in addition to the high energy-saving effect, it also has high internal volume efficiency and meets the demand for space-saving. It is possible to provide an environment-friendly refrigerator with excellent basic functions that can also be met.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a heat insulating box in a first embodiment and a third embodiment of the present invention.

FIG. 2 is a process chart according to a second embodiment of the present invention.

FIG. 3 is a perspective view of a refrigerator showing a cutout portion according to a fourth embodiment of the present invention.

FIG. 4 is a front sectional view of a refrigerator according to a fifth embodiment of the present invention.

FIG. 5 is a side sectional view of a refrigerator according to a fifth embodiment of the present invention.

FIG. 6 is a sectional view of a vacuum heat insulating material for a refrigerator according to a fifth embodiment of the present invention.

FIG. 7 is a sectional view of a vacuum heat insulating material for a refrigerator according to a sixth embodiment of the present invention.

FIG. 8 is a front sectional view of a refrigerator according to a seventh embodiment of the present invention.

FIG. 9 is a side sectional view of a refrigerator according to a seventh embodiment of the present invention.

[Explanation of symbols]

1 Insulation box 2 inner box 3 outer box 5 rigid urethane foam 6 vacuum insulation 7 Crushing process 8 Sorting process 9 Foam insulation treatment process 10 Raw material manufacturing process 11 Raw material manufacturing process 12 refrigerator 101 Refrigerator body 102,122 Insulation box 103 door 105 outer box 107 rigid urethane foam 108,120,121 Vacuum insulation 109 Freezing room (cooling room) 110 Cold room (cooling room) 111 Vegetable room (cooling room) 116 Inorganic fiber aggregate

Front page continuation (72) Inventor Shohashi Ohashi 4-2-5 Takaidahondori, Higashi-Osaka City, Osaka Prefecture Matsushita Refrigerating Machinery Co., Ltd. (56) References JP-A-8-68591 (JP, A) JP-A 10-212332 (JP, A) JP 63-218724 (JP, A) JP 2000-247917 (JP, A) JP 2000-312875 (JP, A) JP 63-187084 (JP, A) JP-A 11-257581 (JP, A) JP-A 62-217087 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) F25D 23/08

Claims (21)

(57) [Claims] 1. The flexural modulus of elasticity is 8.0 MPa or more and the density is 60 kg / m ³ or less so that the rigidity strength and the heat insulation performance are improved.
A heat-insulating box body comprising the secured rigid urethane foam and a vacuum heat-insulating material, and the coverage of the vacuum heat-insulating material exceeds 50% of the surface area of the outer box. 2. A flexural modulus of 8.5 to 10.0 MPa.
And a urethane foam with a density of 45 to 55 kg / m3
And a vacuum insulation material, the vacuum insulation material being coated
A heat-insulating box whose rate exceeds 50% of the outer box surface area. 3. The flexural modulus of elasticity is 8.0 MPa or more and the density is 60 kg / m ³ or less so that the rigidity strength and the heat insulation performance are improved.
A heat insulating box body comprising the secured rigid urethane foam and a vacuum heat insulating material, the coverage of the vacuum heat insulating material exceeds 40% of the surface area of the outer box, and has three or more doors. 4. A flexural modulus of 8.5 to 10.0 MPa.
And a urethane foam with a density of 45 to 55 kg / m3
And a vacuum insulation material, the vacuum insulation material being coated
The rate exceeds 40% of the surface area of the outer box and there are 3 or more doors.
Insulation box body to do. 5. A isocyanate component rigid polyurethane foam is made of a tolylene diisocyanate composition, a polyol, a foam stabilizer, a catalyst, claim 1, characterized in that a premix component consisting of foaming agent may be mixed reaction
The heat insulating box according to any one of 4 above. 6. A heat-insulating main body according to any one claim of claims 1-5 in which the blowing agent comprises water. 7. A crushing step of crushing the heat-insulating box according to any one of claims 1 to 6 , and a waste piece crushed by this crushing step is charged, and iron, non-ferrous metal, resin dust, etc. It is obtained by a sorting treatment step of sorting into, a foam insulation material treatment step of pulverizing a hard urethane foam block separated from waste in the crushing step by crushing, compression, etc., and a foam insulation material treatment step. The hard urethane foam powder is liquefied by an aminolysis reaction or a glycolysis reaction, and after removing resin fine particles and crushed metal fine particles as impurities, it is chemically treated by a reaction with supercritical water or subcritical water. The raw material group produced by the waste treatment method, which consists of a raw material compound of rigid urethane foam and a raw material production process that decomposes into multiple amines, is used in the raw material production process. A method for producing a raw material, which comprises fractionating and distilling and synthesizing tolylenediisocyanate composition and tolylenediamine-based polyether polyol from tolylenediamine which is one of the fractional components. 8. A polyether polyol or tolylene diisocyanate composition obtained by the method for producing a raw material according to claim 7 is used as a raw material, and a foam stabilizer, a catalyst and a foaming agent are mixed and injected between an inner box and an outer box. , A heat-insulating box body made of hard urethane foam by foaming and hardening. 9. The refrigerator according to any one of claims 1, which is to display the raw materials type of rigid polyurethane foam 6 and 8. 10. A refrigerator according to any one claim of the raw materials type of rigid polyurethane foam from claim 1, was recorded 6 and 8. 11. The coverage is more than 50% of the surface area of the outer box,
Vacuum insulation of 80% or less and flexural modulus of 8.0MP
Rigid and strong with a or more and density of 60 kg / m3 or less
And a gas barrier film covering the core material, wherein the vacuum insulation material is a sheet-shaped inorganic material having a plurality of layers. An insulating box made of fiber aggregate. 12. The coverage exceeds 50% of the surface area of the outer box,
80% or less vacuum insulation material and flexural modulus 8.5-1
Hardness of 0.0 MPa and density of 45-55 kg / m3
A heat-insulating box body made of high quality urethane foam, comprising:
Vacuum insulation material and gas barrier film covering the core material and the core material
Sheet-shaped inorganic fiber collection having a plurality of layers
A heat-insulating box made of united body. 13. The vacuum heat insulator sides, top, rear, claim 11 or 12 arranged bottom, and front of each side
Insulated box body described. 14. The entire thickness of the heat insulating wall except for a door formed of a rigid urethane foam and a vacuum heat insulating material is 20 mm to 5 mm.
The heat insulating box body according to any one of claims 11 to 13, which has a length of 0 mm. 15. The entire insulation wall thickness is 20 mm to 50 m except for the hard urethane foam and the vacuum insulation material in the region where the temperature inside the insulation box is maintained at the freezing temperature.
The heat-insulating box body according to any one of 11 to 13 in which m is set. 16. The thickness of the heat insulating wall is 20 mm to 40 m except for a door formed of a rigid urethane foam and a vacuum heat insulating material in a region where the temperature inside the heat insulating box is maintained at a refrigerating temperature.
The heat-insulating box body according to any one of 11 to 13 in which m is set. 17. The vacuum heat insulating material has a thickness of 10 mm to 20 m.
The heat-insulating box body according to any one of claims 14 to 16 , wherein m is m. 18. When the thermal conductivity of the rigid urethane foam is 0.015 W / mK, the thermal conductivity of the vacuum heat insulating material is 0.0010 W / mK to 0.0030 W / mK, and 1/15 to 1/5. The ratio of claim 11 to 17
The heat insulating box according to any one of 1. From 19. Claim 11 which is disposed embedded in rigid urethane foam the vacuum heat insulating material intermediate the outer box and the inner box 1
The heat insulating box according to any one of 3 above. 20. A vacuum heat insulating material is embedded and arranged in a rigid urethane foam between the outer box and the inner box on the side surface of the heat insulating box, and the vacuum heat insulating material is provided on a door, a back surface and a bottom surface.
When it is provided, it is provided in an outer box.
The heat insulating box according to any one of 1 . 21. A heat insulating box according to any one of claims 11 to 20, a cooling chamber formed in the heat insulating box, and a cooling device for cooling the cooling chamber. refrigerator.