CN100516624C - Heat-insulating housings and preparation method thereof - Google Patents
Heat-insulating housings and preparation method thereof Download PDFInfo
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- CN100516624C CN100516624C CNB2007101044079A CN200710104407A CN100516624C CN 100516624 C CN100516624 C CN 100516624C CN B2007101044079 A CNB2007101044079 A CN B2007101044079A CN 200710104407 A CN200710104407 A CN 200710104407A CN 100516624 C CN100516624 C CN 100516624C
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- hard polyurethane
- vacuum heat
- insulating plate
- polyurethane fat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
- B29C44/18—Filling preformed cavities
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D23/00—General constructional features
- F25D23/06—Walls
- F25D23/062—Walls defining a cabinet
- F25D23/064—Walls defining a cabinet formed by moulding, e.g. moulding in situ
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L59/00—Thermal insulation in general
- F16L59/06—Arrangements using an air layer or vacuum
- F16L59/065—Arrangements using an air layer or vacuum using vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2201/00—Insulation
- F25D2201/10—Insulation with respect to heat
- F25D2201/12—Insulation with respect to heat using an insulating packing material
- F25D2201/126—Insulation with respect to heat using an insulating packing material of cellular type
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2201/00—Insulation
- F25D2201/10—Insulation with respect to heat
- F25D2201/14—Insulation with respect to heat using subatmospheric pressure
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D23/00—General constructional features
- F25D23/08—Parts formed wholly or mainly of plastics materials
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B40/00—Technologies aiming at improving the efficiency of home appliances, e.g. induction cooking or efficient technologies for refrigerators, freezers or dish washers
Landscapes
- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Refrigerator Housings (AREA)
- Polyurethanes Or Polyureas (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
- Thermal Insulation (AREA)
Abstract
The purpose of the present invention exists in, ensure the favorable external appearance and no unfilled space cavity in the heat-insulated box body to exert the heat insulation character of the vacuum thermal insulated plate. The heat-insulated box body (7) is arranged with vacuum thermal insulated plate (12) in the space of the box body (7A) which is formed by the external box (13) and the inner box (14), and is filled with hard polyurethane foam (11). The heat-insulated box body uses the combined aerating power which is combined with 1.5 to 1.8 weight-share of water and 13 to 15 weight-share of cyclopentane in the 100 weight-share composed of relative energizing agent, lather booster and polyol combination, makes it become the hard polyurethane foam reacted from the polyatomic alcohol component which comprises more than 40 percent of the mixture whose solubility is low in the cyclopentane, make the flowing thickness of the polyurethane on the vacuum thermal insulated plate to more than two times of the thickness of the vacuum thermal insulated plate, arrange the vacuum thermal insulated plate above the position which is 20 mm distance to the injection port (6), fill in the hard polyurethane foam.
Description
Technical field
The present invention relates to body of thermal insulating box and manufacture method thereof, especially be suitable for body of thermal insulating box and manufacture method thereof on refrigerator, freezer, refrigerator display case and the vending machine etc.
Background technique
In recent years, wish to save energy strongly from the viewpoint that prevents global warming, economizing energy at any realm section all becomes problem, and the viewpoint from effective utilization of heat requires the body of thermal insulating box with good heat-insulating property.
So, proposed and used the body of thermal insulating box of the low vacuum heat-insulating plate of hard polyurethane fat foam and thermal conductivity as heat insulation layer, for example, the spy opens 2000-283385 communique (patent documentation 1), spy and opens the scheme that 2001-99392 communique (patent documentation 2), spy are opened the described body of thermal insulating box of 2002-90048 communique (patent documentation 3).
These body of thermal insulating box be form by outer container and in the casing that constitutes of case, and fill the body of thermal insulating box of hard polyurethane fat foam in the space between outer container that is formed at this casing and interior case under the state of configuration vacuum heat-insulating plate.
In addition, about hard polyurethane fat foam, follow the Kazakhstan dragon restriction of stabilizer, in the depletion of the ozone layer coefficient is zero carbon compound, the thermal conductivity of gas is low, and the cyclopentane with the boiling point that is suitable for hard polyurethane fat foam foaming becomes main flow as stabilizer.
In recent years, because the unevenness between supply and demand of the polyurethane raw material in the surging and worldwide of crude oil price etc., produce the problem such as surging of the in short supply of worldwide polyurethane raw material and polyurethane cost of material.
So, can consider perhaps to narrow down corresponding to the space of vacuum heat-insulating plate by the thickening vacuum heat-insulating plate, the packed space of dwindling hard polyurethane fat foam reduces the polyurethane raw material.But, if do like this, it is contemplated that vacuum heat-insulating plate becomes obstacle, for the hard polyurethane fat foam that flow that will in removing the space of vacuum heat-insulating plate, foam, become strict condition.For example, it is contemplated that, along with the rapid change of the adiabatic thickness of the hard polyurethane fat foam at the position of having carried vacuum heat-insulating plate and produce following problem, that is: hard polyurethane fat foam shrink and with its bonding outer container bad local deformation are taken place, perhaps because the not generation of filling part and the decline of following its heat-insulating property of the part of the hard polyurethane fat foam that hard polyurethane fat foam cause the obstruction that flows, the perhaps generation of the bad local deformation of the outer container that generation caused in the space, top layer that causes etc. because hard polyurethane fat foam irregular flows.
Summary of the invention
The object of the present invention is to provide a kind of good surface appearance state of the body of thermal insulating box that can guarantee to carry vacuum heat-insulating plate and do not have unfilled space and brought into play the insulating characteristics of vacuum heat-insulating plate, and, can suppress the body of thermal insulating box and the manufacture method thereof of the use amount of hard polyurethane fat foam.
In order to achieve the above object, the body of thermal insulating box of first scheme of the present invention is, be formed at by outer container and in the casing that constitutes of case above-mentioned outer container and above-mentioned in disposed in the space between the case in the body of thermal insulating box of filling hard polyurethane fat foam under the state of vacuum heat-insulating plate, it is characterized in that, use is at relative catalyzer, surfactant, polyol blends 100 weight portions have made up in the mixed foaming agent of cyclopentane of the water of 1.2～2.0 weight portions and 13～15 weight portions, make hard polyurethane fat foam as polyol component with the low mixture of ingredients of the above dissolubility of 40 weight % and isocyanate prepolymer composition reaction with cyclopentane, the mobile gap of above-mentioned hard polyurethane fat foam as the face that is provided with above-mentioned vacuum heat-insulating plate that is formed at the space between above-mentioned outer container and the above-mentioned interior case, guarantee that the gap is more than 2 times of thickness of above-mentioned vacuum heat-insulating plate, above-mentioned vacuum heat-insulating plate is configured in the above-mentioned casing, make that the distance with this inlet of end back gauge of the nearest above-mentioned vacuum heat-insulating plate of the inlet that is used to fill above-mentioned hard polyurethane fat foam is more than the 20mm, and fill above-mentioned hard polyurethane fat foam.
The body of thermal insulating box of relevant first scheme of the present invention, preferred concrete configuration example is as follows:
(1) having used apart from the distance of the inlet of above-mentioned hard polyurethane fat foam is 30～33kg/m as the global density of the periostracum of the hard polyurethane fat foam more than the 500mm
3, compression strength is more than the 0.1MPa, the size changing rate in air after 70 ℃ of temperature with-20 ℃ are placed 24 hours is the above-mentioned hard polyurethane fat foam below 1.0%.
(2) vacuum heat-insulating plate that uses as above-mentioned vacuum heat-insulating plate possesses: the inorfil congeries that will not comprise tackiness agent is contained in the core in the inner bag that is made of monomer or plastic pellicle; And the outsourcing material that constitutes by laminated film that holds above-mentioned core, reduced pressure and periphery is carried out deposited sealing in inside.
In order to achieve the above object, the manufacture method of the body of thermal insulating box of alternative plan of the present invention is, the casing that case constitutes in formation is reached by outer container, the above-mentioned outer container that is formed at this casing and above-mentioned in disposed in the space between the case and fill hard polyurethane fat foam under the state of vacuum heat-insulating plate and form in the manufacture method of body of thermal insulating box of body of thermal insulating box, its feature is being, use is at relative catalyzer, surfactant, polyol blends 100 weight portions have made up in the mixed foaming agent of cyclopentane of the water of 1.2～2.0 weight portions and 13～15 weight portions, make hard polyurethane fat foam as polyol component with the low mixture of ingredients of the above dissolubility of 40 weight % and isocyanate prepolymer composition reaction with cyclopentane, the mobile gap of above-mentioned hard polyurethane fat foam as the face that is provided with above-mentioned vacuum heat-insulating plate that is formed at the space between above-mentioned outer container and the above-mentioned interior case, guarantee that the gap is more than 2 times of thickness of above-mentioned vacuum heat-insulating plate, above-mentioned vacuum heat-insulating plate is configured in the above-mentioned casing, make that the distance with this inlet of end back gauge of the nearest above-mentioned vacuum heat-insulating plate of the inlet that is used to fill above-mentioned hard polyurethane fat foam is more than the 20mm, and fill above-mentioned hard polyurethane fat foam.
The manufacture method of the body of thermal insulating box of relevant alternative plan of the present invention, preferred concrete formation example is as follows:
(1) having used apart from the distance of the inlet of above-mentioned hard polyurethane fat foam is 30～33kg/m as the global density of the periostracum of the hard polyurethane fat foam more than the 500mm
3, compression strength is more than the 0.1MPa, the size changing rate in air after 70 ℃ of temperature with-20 ℃ are placed 24 hours is the above-mentioned hard polyurethane fat foam below 1.0%.
(2) vacuum heat-insulating plate that uses as above-mentioned vacuum heat-insulating plate possesses: the inorfil congeries that will not comprise tackiness agent is contained in the core in the inner bag that is made of monomer or plastic pellicle; And the outsourcing material that constitutes by laminated film that holds above-mentioned core, reduced pressure and periphery is carried out deposited sealing in inside.
The present invention has following effect.
According to the present invention, a kind of good surface appearance state of the body of thermal insulating box that can guarantee to carry vacuum heat-insulating plate can be provided and not have unfilled space and brought into play the insulating characteristics of vacuum heat-insulating plate, and, can suppress the body of thermal insulating box and the manufacture method thereof of the use amount of hard polyurethane fat foam.
Description of drawings
Fig. 1 is that two kinds of liquid that pass through polyatomic alcohol polybasic alcohol and isocyanates that the body of thermal insulating box that is used for an embodiment of the invention is described mix the schematic diagram that generates hard polyurethane fat foam.
Fig. 2 is the ideograph of occupid state of hard polyurethane fat foam of the body of thermal insulating box of explanation present embodiment.
Fig. 3 is the major component sectional view by the body of thermal insulating box of present embodiment manufacturing.
Fig. 4 is the perspective ideograph of the body of thermal insulating box of present embodiment.
Among the figure:
The 1-polyatomic alcohol polybasic alcohol; The 2-isocyanates; The 3-mixing head; 5-polyurethane stoste; The 6-inlet;
The 7-body of thermal insulating box; The 7A-casing; The 8-refrigerator product back side; The 9-injection head;
The cutting sample of 10-hard polyurethane fat foam; 11-hard polyurethane fat foam;
The 12-vacuum heat-insulating plate; The 13-outer container; Case in the 14-.
Embodiment
Below, use Fig. 1～Fig. 4 that the body of thermal insulating box and the manufacture method thereof of an embodiment of the invention are described.The body of thermal insulating box of present embodiment is the example of refrigerator with body of thermal insulating box.
The body of thermal insulating box of present embodiment forms the casing 7A that is made of outer container 13 and interior case 14, fills hard polyurethane fat foam 11 in the space between outer container 13 that is formed at this casing 7A and interior case 14 under the state of configuration vacuum heat-insulating plate 12.
And, in the present embodiment, use and in catalyzer, surfactant, polyol blends 100 weight portions have relatively made up the mixed foaming agent of cyclopentane of the water of 1.5～1.8 weight portions and 13～15 weight portions, to make as the polyol component with the low mixture of ingredients of dissolubility more than the 40 weight % and the hard polyurethane fat foam of isocyanate prepolymer composition reaction with cyclopentane.Also have, in the present embodiment, the gap of flowing as hard polyurethane fat foam on the face that vacuum heat-insulating plate 12 is set in the space between outer container 13 that is formed at casing 7A and the interior case 14 11 (polyurethane flow thickness) T, the gap more than 2 times of guaranteeing the thickness t of vacuum heat-insulating plate 12.Have again, in the present embodiment, vacuum heat-insulating plate 12 is configured in the casing 7A, the position of the limit portion of the vacuum heat-insulating plate 12 that the inlet that makes and be used to fill hard polyurethane fat foam 11 6 is nearest is more than the 20mm apart from the distance of this hard polyurethane fat foam inlet 6, and fills hard polyurethane fat foam 11 under this state.
According to present embodiment, a kind of good surface appearance state of the body of thermal insulating box 7 that can guarantee to carry vacuum heat-insulating plate 12 can be provided and not have the insulating characteristics of ground performance vacuum heat-insulating plates 12 such as unfilled space, and, can suppress the body of thermal insulating box and the manufacture method thereof of the use amount of hard polyurethane fat foam 11.Below explanation can obtain the concrete reason of this effect.
The body of thermal insulating box of present embodiment and manufacture method thereof are as shown in Figure 1, the two kinds of soln using mixing heads 3 that accumulate in polyatomic alcohol polybasic alcohol 1 in the different containers and isocyanates 2 are stirred, as shown in Figure 2, the polyurethane stoste 5 that stirred is injected into casing 7A as object from injection head 9 in.
Inject the occasion of polyurethane stoste 5 in casing 7A, as shown in Figure 2, under the back side 8 state up that makes casing 7A, the inlet 6 in four places, bight by being formed at this back side 8 carries out.Corresponding these inlet 6 configuration injection heads 9.In addition, as shown in Figures 3 and 4, by bonding or adhesive tape etc. vacuum heat-insulating plate 12 is sticked on the rear side of outer container 13 in advance.
As shown in Figure 2, polyurethane stoste 5 in injection head 9 is injected into casing 7A is along with after gravity falls downwards, when volume is increased, in casing 7A, float upward, and in whole box body 7A, flow, as shown in Figure 3, be filled in and become hard polyurethane fat foam 11 between outer container 13 or vacuum heat-insulating plate 12 and the interior case 14.
In this foamed process,, produce the hole part (unfilled space) of not filling hard polyurethane fat foam 11 if, then produce flow obstacle because vacuum heat-insulating plate 12 narrows down the space that hard polyurethane fat foam 11 flow.If the hole part takes place, then product is recessed and have problems in appearance, simultaneously, makes heat leakage in the refrigerator to outside by this hole part, thereby produces the problem that the power consumption of refrigerator increases.
So, in the body of thermal insulating box 7 of Fig. 2～shown in Figure 4, for the vacuum heat-insulating plate 12 that carries maximum area, and the lateral parts of the body of thermal insulating box 7 that its outward appearance also arouses attention easily in the time of can thinking to use, with regard to the relation of the mobile thickness of the thickness of vacuum heat-insulating plate 12 and hard polyurethane fat foam 11, with a plurality of example comparative evaluations have or not these three key elements of unfilled space, thermal conductivity and density of hard polyurethane fat foam 11.
Its evaluation result of table 1 expression.Here, as shown in Figure 3, the thickness size of establishing vacuum heat-insulating plate 12 is t, and the thickness size of establishing the space that is formed by case 14 in vacuum heat-insulating plate 12 and the refrigerator is T.In addition, the hard polyurethane fat foam 11 that use in this evaluation have utilized the material of pursuit as the prescription of the thermal conductivity of the index of the heat-insulating property of refrigerator.And, in experiment, measured the thermal conductivity, the global density and the central part density of cutting sample 10 (with reference to Fig. 2) of hard polyurethane fat foam 11 of getting the sample of 50mm * 50mm from the appropriate section of the refrigerator of reality of cutting sample 10 (with reference to Fig. 2) of hard polyurethane fat foam 11 that has or not and get the sample of 200mm * 200mm from the appropriate section of the refrigerator of reality in unfilled space of the lateral parts of body of thermal insulating box 7.
Table 1
| Vacuum insulation thickness t (mm) | Polyurethane flow thickness T (mm) | Voidlessness is arranged | Thermal conductivity (mW/mK) | Global density-central part density (kg/m 3) | |
| Conventional example 1 | - | 35 | Do not have | 18.5 | 2.9 |
| Comparative example 1 | 5 | 8 | Have | 20.2 | 5.3 |
| Embodiment 1 | 5 | 10 | Do not have | 18.7 | 3.2 |
| |
5 | 15 | Do not have | 18.5 | 3.4 |
| Comparative example 2 | 10 | 15 | Have | 19.6 | 5.1 |
| |
10 | 20 | Do not have | 18.6 | 3.5 |
| |
10 | 25 | Do not have | 18.5 | 3.3 |
| Comparative example 3 | 15 | 10 | Have | 19.4 | 5.1 |
| |
15 | 30 | Do not have | 18.5 | 3.4 |
| |
15 | 40 | Do not have | 18.6 | 3.4 |
Conventional example 1
The conventional example 1 of table 1 is not carry vacuum heat-insulating plate, and the mobile thickness T of hard polyurethane fat foam 11 is set at the example of 35mm.In this conventional example 1, when making 11 foaming of hard polyurethane fat foam, near appropriate section, do not observe unfilled space, thermal conductivity is 18.5mW/mK down at 10 ℃, the numerical value that has deducted central part density from global density is 2.9.Can think that according to above content the state table cortex of conventional example 1 its hard polyurethane fat foam 11 is also thin and good, thermal conductivity also is good numerical value.In addition, because conventional example 1 is not carried vacuum heat-insulating plate, thus compare with the situation of carrying vacuum heat-insulating plate, lower as the heat-insulating property of body of thermal insulating box.
Comparative example 1
The comparative example 1 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 5mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at example (T＜2t=of 8mm.In this comparative example 1, when making hard polyurethane fat foam 11 foaming, near appropriate section, produce unfilled space, thermal conductivity is 20.2mW/mK and not good, the numerical value that has deducted central part density from global density is 5.3 to be higher result.This can think, because the rapid change of the adiabatic thickness of hard polyurethane fat foam 11 is involved in foamed gas when mobile, forms periostracum easily, the state of the foam extreme difference that becomes, and also density also rises partly, thus make the thermal conductivity deterioration.The deterioration of this thermal conductivity produces the problem of the power consumption increase of refrigerator.
Embodiment 1
The embodiment 1 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 5mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at the example (T=2t) of 10mm.In this embodiment 1, when making 11 foaming of hard polyurethane fat foam, near appropriate section, do not produce unfilled space, thermal conductivity is 18.7mW/mK, the numerical value that has deducted central part density from global density is 3.2, and itself becoming with conventional example 1 as hard polyurethane fat foam 11 does not have the very numerical value of big difference.This can think, flowing of hard polyurethane fat foam 11 successfully carried out, and has obtained the intrinsic in essence material performance of hard polyurethane fat foam 11.
The embodiment 2 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 5mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at the example (T＞2t) of 15mm.In this embodiment 2, when making 11 foaming of hard polyurethane fat foam, near appropriate section, do not produce unfilled space, thermal conductivity is 18.5mW/mK, the numerical value that has deducted central part density from global density is 3.4, and becoming with conventional example 1 does not have the very numerical value of big difference.This can think, flowing of hard polyurethane fat foam 11 successfully carried out, and has obtained the intrinsic in essence material performance of actual hard polyurethane fat foam 11.
Comparative example 2
The comparative example 2 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 10mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at example (T＜2t=of 15mm.In this comparative example 2, when making hard polyurethane fat foam 11 foaming, near appropriate section, produce unfilled space, thermal conductivity is 19.6mW/mK and not good, the numerical value that has deducted central part density from global density is 5.1 to be higher result.This can think, because the rapid change of the adiabatic thickness of hard polyurethane fat foam 11 is involved in foamed gas when mobile, forms periostracum easily, the state extreme difference of foam, and also density also rises partly, thus thermal conductivity is worsened.
The embodiment 3 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 10mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at the example (T=2t) of 20mm.In this embodiment 3, when making 11 foaming of hard polyurethane fat foam, near appropriate section, do not produce unfilled space, thermal conductivity is 18.6mW/mK, the numerical value that has deducted central part density from global density is 3.5, and itself becoming with conventional example 1 as hard polyurethane fat foam 11 does not have the very numerical value of big difference.This can think, flowing of hard polyurethane fat foam 11 successfully carried out, and has obtained the intrinsic in essence material performance of hard polyurethane fat foam 11.
The embodiment 4 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 10mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at the example (T＞2t) of 25mm.In this embodiment 4, when making 11 foaming of hard polyurethane fat foam, near appropriate section, do not produce unfilled space, thermal conductivity is 18.5mW/mK, the numerical value that has deducted central part density from global density is 3.3, though a difference is arranged a little, becoming with conventional example 1 does not have the very numerical value of big difference.This can think, flowing of hard polyurethane fat foam 11 successfully carried out, and has obtained the intrinsic in essence material performance of hard polyurethane fat foam 11.
Comparative example 3
The comparative example 3 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 15mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at example (T＜2t=of 10mm.In this comparative example 3, when making hard polyurethane fat foam 11 foaming, near appropriate section, produce unfilled space, thermal conductivity is 19.4mW/mK and not good, the numerical value that has deducted central part density from global density is 5.1 to become higher result.This can think, because the rapid change of the adiabatic thickness of hard polyurethane fat foam 11 is involved in foamed gas when mobile, forms periostracum easily, the state of the foam extreme difference that becomes, and also density also rises partly, thus make the thermal conductivity deterioration.
The embodiment 5 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 15mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at the example (T=2t) of 30mm.In this embodiment 5, when making 11 foaming of hard polyurethane fat foam, near appropriate section, do not produce unfilled space, thermal conductivity is 18.5mW/mK, the numerical value that has deducted central part density from global density is 3.4, and itself becoming with conventional example 1 as hard polyurethane fat foam 11 does not have the very numerical value of big difference.This can think, flowing of hard polyurethane fat foam 11 successfully carried out, and has obtained the intrinsic in essence material performance of hard polyurethane fat foam 11.
The embodiment 6 of table 1 is that the thickness t with vacuum heat-insulating plate 12 is set at 15mm, and the mobile thickness T of hard polyurethane fat foam 11 is set at the example (T＞2t) of 40mm.In this embodiment 6, when making 11 foaming of hard polyurethane fat foam, near appropriate section, do not produce unfilled space, thermal conductivity is 18.6mW/mK, the numerical value that has deducted central part density from global density is 3.4, and itself becoming with conventional example 1 as hard polyurethane fat foam 11 does not have the very numerical value of big difference.This can think, flowing of hard polyurethane fat foam 11 successfully carried out, and has obtained the intrinsic in essence material performance of hard polyurethane fat foam 11.
From the evaluation result shown in the table 1 as can be known, in the space that is formed between outer container 13 and the interior case 14, disposed under the state of vacuum heat-insulating plate 12, form the occasion of body of thermal insulating box filling hard polyurethane fat foam 11, as the gap that hard polyurethane fat foam 11 flow, need guarantee that this gap is more than 2 times of thickness of vacuum heat-insulating plate 12.
And, in the body of thermal insulating box 7 of Fig. 2～shown in Figure 4, for the vacuum heat-insulating plate 12 that carries maximum area, and the lateral parts of the body of thermal insulating box 7 that its outward appearance also arouses attention easily in the time of can thinking use, with regard to the inlet 6 of hard polyurethane fat foam 1 with to the relation of the distance of the end face of the vacuum heat-insulating plate 12 of a side close with it, with a plurality of example comparative evaluations the side face appearance of outer container 13 situation, the unfilled space that has or not hard polyurethane fat foam 11, these three elements of compressive resistance of being out of shape.
Its evaluation result of table 2 expression.The distance of injecting the end limit of oral-lateral with the most close polyurethane in four limits of inlet 6 and vacuum heat-insulating plate 12 is made as L here.In addition, the hard polyurethane fat foam 11 that use in this evaluation have utilized the material of pursuit as the prescription of the thermal conductivity of the index of the heat-insulating property of refrigerator.In addition, in experiment, remaining in when placing 8 hours in-10 ℃ the Constant Low Temperature Facilities distortion of refrigerator side appropriate section is being observed, appropriate section to the refrigerator of reality has or not the space on top layer to confirm, and to have measured apart from the distance of the inlet 6 of hard polyurethane fat foam 11 be the compressive resistance that the hard polyurethane fat foam 11 of 50mm * 50mm sample are got at the 30mm place.
Table 2
Conventional example 2
The conventional example 2 of table 2 is not carry vacuum heat-insulating plate, and the example of hard polyurethane fat foam 11 only is set.In conventional example 2, near the outward appearance distortion of inlet 6 is not seen showy space, top layer in order yet, and the compressive resistance of hard polyurethane fat foam 11 is 0.15Mpa, has shown good numerical value.
Comparative example 4
The comparative example 4 of table 2 is that the distance L on the end limit of inlet 6 and vacuum heat-insulating plate 12 is the example (L=0) of 0mm.In this comparative example 4, because the end limit of inlet 6 and vacuum heat-insulating plate 12 is consistent, thereby consequently, observes bigger distortion near inlet 6, also disperse to exist the space, top layer, compressive resistance is little of 0.07Mpa, and foamy body is very poor.
This can think, since the mobile thickness T of hard polyurethane fat foam 11 because of vacuum heat-insulating plate 12 partly attenuation beginning foaming place attenuation partly, thereby be easy to generate contraction owing to the abscess of hard polyurethane fat foam 11 extends at the step place of adiabatic thickness, become and make outer container produce the main cause of the distortion of appearance.And near the inlet 6 of hard polyurethane fat foam 11, because the splashing or steep last polyurethane stoste to splashing of outer container etc. of the stoste of the last polyurethane of bubble when injecting, the 11 easy roughening of hard polyurethane fat foam are easy to generate the space, top layer.Especially can think,, then be easy to generate the space, top layer if the end limit of inlet 6 and vacuum heat-insulating plate 12 is overlapping.If produce this space, top layer, when then producing the recessed apparent problem of product, the heat in the refrigerator just is lost to the outside from this hole portion, produces the problem that the power consumption of refrigerator increases.
Comparative example 5
The comparative example 5 of table 2 is that the distance L on the end limit of inlet 6 and vacuum heat-insulating plate 12 is the example (L=10) of 10mm.The result of this comparative example 5 is, near inlet 6, observes distortion, and also disperseing to have space, top layer, compressive resistance is 0.10Mpa, and foamy body is poor slightly.
Comparative example 6
The comparative example 6 of table 2 is that the distance L on the end limit of inlet 6 and vacuum heat-insulating plate 12 is the example (L=15) of 15mm.The result of this comparative example 6 is, near inlet 6, observes less distortion, also has some less spaces, top layer.On the other hand, the compressive resistance of hard polyurethane fat foam 11 is 0.13MPa, becomes the value approaching with conventional example 2.
The comparative example 7 of table 2 is that the distance L on the end limit of inlet 6 and vacuum heat-insulating plate 12 is the example (L=20) of 20mm.In this comparative example 7, though its adiabatic thickness attenuation partly of vacuum insulation plate portion, owing to guaranteed mobile distance apart from inlet 6, thereby the viscosity increase of polyurethane is not had big influence, there is not the generation in big space yet.It can be said that, can provide a kind of and guarantee comparison good surface appearance state, and not have unfilled space, and can bring into play the insulating characteristics of vacuum heat-insulating plate, be i.e. the little refrigerator of consumes power.In addition, measuring when the distance of the inlet 6 of hard polyurethane fat foam 11 is the compressive resistance of polyurethane foam 11 of 30mm place sampling, its value is 0.15MPa, for the equal numerical value of the conventional example 2 that vacuum heat-insulating plate is not set.
The embodiment 8 of table 2 is that the distance L on the end limit of inlet 6 and vacuum heat-insulating plate 12 is the example (L=25) of 25mm.In this embodiment 8, though its adiabatic thickness attenuation partly of vacuum insulation plate portion, the mobile distance owing to having guaranteed from inlet 6 so the viscosity increase of polyurethane is not had big influence, does not have the generation in bigger space yet.It can be said that, can provide a kind of and guarantee comparison good surface appearance state, and not have unfilled space etc., and can bring into play the insulating characteristics of vacuum heat-insulating plate, be i.e. the little refrigerator of consumes power.In addition, when having measured distance at the inlet 6 of distance hard polyurethane fat foam 11 and be the compressive resistance of polyurethane foam 11 of 30mm place sampling, its value is 0.15MPa, for the equal numerical value of the conventional example 2 that vacuum heat-insulating plate is not set.
From the evaluation result shown in the table 2 as can be known, in the space that is formed between outer container 13 and the interior case 14, disposed under the state of vacuum heat-insulating plate 12, fill hard polyurethane fat foam 11 and the occasion of formation body of thermal insulating box, vacuum heat-insulating plate 12 need be configured in the casing 7A, make that the distance with the end back gauge inlet of the nearest vacuum heat-insulating plate 12 of inlet 6 is more than the 20mm, and under this state, fill hard polyurethane fat foam 11.
Have again, cooperate for the composition of the material of hard polyurethane fat foam 11, with a plurality of example comparative evaluations global density, compression strength, low temperature size changing rate, high temperature size changing rate, thermal conductivity, these six key elements of foam state.
Its evaluation result of table 3 expression.Here, use is polyether polyol (being called polyatomic alcohol polybasic alcohol A) with the toluylenediamine of propylene oxide addition, ortho-toluene diamine with the propylene oxide addition is polyether polyol (being called polyatomic alcohol polybasic alcohol B), triethanolamine with the propylene oxide addition is polyether polyol (being called polyatomic alcohol polybasic alcohol C), sucrose with the propylene oxide addition is polyether polyol (being called polyatomic alcohol polybasic alcohol D), polyols blend composition 100 weight portions of polyester polyol (being called polyol E), make water and cyclopentane as stabilizer, add catalysts and surfactant therein, use the polymethylene polyphenyl vulcabond as isocyanate prepolymer composition, be infused in the actual refrigerator by 4 shown in Figure 2 and carry out filling-foam, made hard polyurethane fat foam 11.
In addition, each the material performance and the characteristic of his-and-hers watches 3 are discussed below.
Global density: from the distance of distance inlet 6 is part sampling more than the 500mm, measures the weight (A) of hard polyurethane fat foam 11 of the band periostracum of 50mm * 50mm * 35tmm.Be determined in the beaker volume (B) when flooding with distilled water and metal needle, the value that will remove weight (A) with volume (B) density is as a whole estimated.
Compression strength: will be the part sampling more than the 500mm from the distance of distance inlet 6, and be cut to the hard polyurethane fat foam 11 of 50mm * 50mm * 20～25tmm, with transfer rate 4mm/min is load, will estimate as compression strength with the value of original 10% o'clock load of compression area removal distortion.
The low temperature size changing rate: having estimated will be part sampling more than the 500mm from the distance of distance inlet 6, and be cut to the thickness size variance ratio of hard polyurethane fat foam when placing 24 hours down for-20 ℃ of 150mm * 300mm * 20～25tmm.
The high temperature size changing rate: having estimated will be part sampling more than the 500mm from the distance of distance inlet 6, and be cut to the thickness size variance ratio of hard polyurethane fat foam when placing 24 hours down for 70 ℃ of 150mm * 300mm * 20～25tmm.
Thermal conductivity: will be the part sampling more than the 500mm from the distance of distance inlet 6, and be cut to the hard polyurethane fat foam 11 of 200mm * 200mm * 20～25tmm, use the great smart machine society's system HC-071 type of English (heat flow meter method, 10 ℃ of mean temperatures) to estimate.
Foam state: is the state of the part more than the 500mm by visual judgement apart from the distance of inlet 6.
Table 3
| Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | |
|
|
|
| Polyatomic alcohol polybasic alcohol A | 60 | 30 | 0 | 40 | 40 | 40 | 40 |
| Polyatomic alcohol polybasic alcohol B | 0 | 30 | 35 | 0 | 0 | 0 | 0 |
| Polyatomic alcohol polybasic alcohol C | 20 | 30 | 30 | 35 | 20 | 20 | 5 |
| Polyatomic alcohol |
5 | 0 | 10 | 15 | 20 | 20 | 45 |
| Polyol E | 15 | 10 | 25 | 10 | 20 | 20 | 10 |
| Cyclopentane | 18 | 16 | 14 | 12 | 15 | 15 | 14 |
| Water | 0.5 | 1.1 | 1.4 | 1.2 | 1.5 | 1.8 | 1.8 |
| Global density (kg/m 3) | 40.7 | 34.8 | 36.9 | 37.1 | 35.3 | 33.1 | 32.8 |
| Compression strength (MPa) | 0.12 | 0.12 | 0.12 | 0.11 | 0.12 | 0.07 | 0.11 |
| Low temperature size changing rate (%) | -1.19 | -1.32 | -1.24 | -1.36 | -1.05 | -0.95 | -0.86 |
| High temperature size changing rate (%) | 2.25 | 0.88 | 0.96 | 0.85 | 1.21 | 0.75 | 0.73 |
| Thermal conductivity | ○ | ○ | ○ | △ | ○ | ○ | ○ |
| Foam state | ○ | △ | △ | ○ | ○ | ○ | ○ |
Comparative example 6
The comparative example 6 of table 3 is in the polyols blend that has cooperated 60 parts of polyatomic alcohol polybasic alcohol A, 20 parts of polyatomic alcohol polybasic alcohol C, 5 parts of polyatomic alcohol polybasic alcohol D, 15 parts of polyol Es, add water and 18 parts of cyclopentane of 0.5 part, other auxiliary agent and isocyanate solution are reacted and the example of foaming as stabilizer.This cooperation is to reduce the moisture content number for the generation that suppresses carbon dioxide, increases the cyclopentane umber and the combination that improves foaming efficient, is special in to improve the combination of thermal conductivity.
Its result, global density increases, and injection amount increases.This can think, because the moisture content number is few, and makes the result of the flowability shortage of hard polyurethane fat foam 11.And the dimensional stability aspect might make the high temperature size changing rate big, and foaming properties can be passed and deterioration in time.
Comparative example 7
The comparative example 7 of table 3 is that relatively example 6 is that polyatomic alcohol polybasic alcohol A reduces by half, and has increased polyatomic alcohol polybasic alcohol B newly, and the water yield also is increased to 1.1 parts, the umber of cyclopentane is taken as 16 parts example.Its result, in comparative example 7, relatively example 6, though the global density step-down, the low temperature size changing rate increases, and, seen the space, top layer at foam surface.Depression and the distortion with outer container in the refrigerator of reality of space, top layer is relevant.
Comparative example 8
The comparative example 8 of table 3 is examples 7 relatively, does not have polyatomic alcohol polybasic alcohol A, is that the center cooperates with polyatomic alcohol polybasic alcohol B, and the water yield is increased to 1.4 parts, cyclopentane is kept to 14 parts example.Its result, in comparative example 8, relatively example 6, though the global density step-down, the low temperature size changing rate increases, and, seen the space, top layer at foam surface.
According to above content, owing to cooperate polyatomic alcohol polybasic alcohol B might produce the space, top layer, thereby in embodiment 9～11 enforcement, do not cooperate polyatomic alcohol polybasic alcohol B.
Comparative example 9
The comparative example 9 of table 3 is examples 6 relatively, and polyatomic alcohol polybasic alcohol A is reduced some and is taken as 40 parts, increases polyatomic alcohol polybasic alcohol C and polyatomic alcohol polybasic alcohol D, and the water yield is taken as 1.2 parts, and the cyclopentane amount is kept to 12 parts example.
Its result, in comparative example 9, relatively example 6, though the global density step-down, it is big that thermal conductivity becomes.If it is big that thermal conductivity becomes, then the deterioration with the cooling capacity of actual refrigerator is relevant.
In the embodiment 9 of table 3, in order to improve thermal conductivity, the umber of cyclopentane is increased to 15 parts.And, increased the amount of polyol E and cooperated the polyol component low with the intermiscibility of cyclopentane, make it account for 40 weight % of polyol component total amount.And, in order to improve flowability, and the umber of water is increased to 1.5 parts.
Its result, in embodiment 9, relatively example 9, obtained global density, compression strength, low temperature size changing rate, high temperature size changing rate, thermal conductivity, these six performances that key element is all good of foam state.
In the embodiment 10 of table 3, embodiment 9 further is increased to 1.8 parts with the moisture content number relatively, and cooperation in addition maintains the original state.Its result has realized the further reduction to injection amount.But the global density of foam also diminishes, and compression strength also descends thereupon.It is better that dimensional stability becomes.
In the embodiment 11 of table 3, relative embodiment 10 increases the use level with the low polyatomic alcohol polybasic alcohol D of the intermiscibility of cyclopentane, and with respect to the total amount of polyatomic alcohol polybasic alcohol, having cooperated the ratio with the low polyatomic alcohol polybasic alcohol of the intermiscibility of cyclopentane is more than the 50 weight %.Its result has realized the minimizing significantly to injection amount.And though global density diminishes, compression strength is improved significantly and is reached numerical value near comparative example, and dimensional stability also reaches good result.Can think, this be because, increase the low polyatomic alcohol polybasic alcohol of intermiscibility with cyclopentane, the relative cyclopentane of bubble abscess is more insoluble, is adequately sealed in the bubble abscess as the cyclopentane of stabilizer, the plasticization effect in the gentle bubble of the cyclopentane hole becomes littler.In addition, the state of foam, thermal conductivity are also good.
According to the evaluation result shown in the table 3 as can be known, in the space that is formed between outer container 13 and the interior case 14, disposed the occasion of filling hard polyurethane fat foam 11 under the state of vacuum heat-insulating plate 12 and forming body of thermal insulating box, need to use at catalyzer, surfactant, polyol blends 100 weight portions relatively, made up and make in the mixed foaming agent of cyclopentane of the water of 1.2～2.0 weight portions and 13～15 weight portions as having and the polyol component of the low mixture of ingredients of the dissolubility of cyclopentane and the hard polyurethane fat foam 11 of isocyanate prepolymer composition reaction.
Claims (6)
1. body of thermal insulating box, be formed at by outer container and in the casing that constitutes of case above-mentioned outer container and above-mentioned in disposed filling hard polyurethane fat foam under the state of vacuum heat-insulating plate in the space between the case, it is characterized in that,
Use has been made up in the mixed foaming agent of cyclopentane of the water of 1.2～2.0 weight portions and 13～15 weight portions at relatively catalyzer, surfactant, polyol blends 100 weight portions, make hard polyurethane fat foam as polyol component with the low mixture of ingredients of the above dissolubility of 40 weight % and isocyanate prepolymer composition reaction with cyclopentane
As the mobile gap of above-mentioned hard polyurethane fat foam of the face that is provided with above-mentioned vacuum heat-insulating plate that is formed at the space between above-mentioned outer container and the above-mentioned interior case, guarantee that this gap is more than 2 times of thickness of above-mentioned vacuum heat-insulating plate,
Above-mentioned vacuum heat-insulating plate is configured in the above-mentioned casing, makes that the distance with this inlet of end back gauge of the nearest above-mentioned vacuum heat-insulating plate of the inlet that is used to fill above-mentioned hard polyurethane fat foam is more than the 20mm, and fill above-mentioned hard polyurethane fat foam.
2. body of thermal insulating box according to claim 1 is characterized in that,
Having used apart from the distance of the inlet of above-mentioned hard polyurethane fat foam is 30～33kg/m as the global density of the periostracum of the hard polyurethane fat foam more than the 500mm
3, compression strength is more than the 0.1MPa, the size changing rate in air after 70 ℃ of temperature with-20 ℃ are placed 24 hours is the above-mentioned hard polyurethane fat foam below 1.0%.
3. body of thermal insulating box according to claim 1 is characterized in that,
The vacuum heat-insulating plate that uses as above-mentioned vacuum heat-insulating plate possesses: the inorfil congeries that will not comprise tackiness agent is contained in the core in the inner bag that is made of monomer or plastic pellicle; And the outsourcing material that constitutes by laminated film that holds above-mentioned core, reduced pressure and periphery is carried out deposited sealing in inside.
4. the manufacture method of a body of thermal insulating box, the casing that formation is made of outer container and interior case, the above-mentioned outer container that is formed at this casing and above-mentioned in disposed in the space between the case and fill hard polyurethane fat foam under the state of vacuum heat-insulating plate and form body of thermal insulating box, it is characterized in that
Use has been made up in the mixed foaming agent of cyclopentane of the water of 1.2～2.0 weight portions and 13～15 weight portions at relatively catalyzer, surfactant, polyol blends 100 weight portions, make hard polyurethane fat foam as polyol component with the low mixture of ingredients of the above dissolubility of 40 weight % and isocyanate prepolymer composition reaction with cyclopentane
As the mobile gap of above-mentioned hard polyurethane fat foam of the face that is provided with above-mentioned vacuum heat-insulating plate that is formed at the space between above-mentioned outer container and the above-mentioned interior case, guarantee that this gap is more than 2 times of thickness of above-mentioned vacuum heat-insulating plate,
Above-mentioned vacuum heat-insulating plate is configured in the above-mentioned casing, makes that the distance with this inlet of end back gauge of the nearest above-mentioned vacuum heat-insulating plate of the inlet that is used to fill above-mentioned hard polyurethane fat foam is more than the 20mm, and fill above-mentioned hard polyurethane fat foam.
5. the manufacture method of body of thermal insulating box according to claim 4 is characterized in that,
Having used apart from the distance of the inlet of above-mentioned hard polyurethane fat foam is 30～33kg/m as the global density of the periostracum of the hard polyurethane fat foam more than the 500mm
3, compression strength is more than the 0.1MPa, the size changing rate in air after 70 ℃ of temperature with-20 ℃ are placed 24 hours is the above-mentioned hard polyurethane fat foam below 1.0%.
6. the manufacture method of body of thermal insulating box according to claim 4 is characterized in that,
The vacuum heat-insulating plate that uses as above-mentioned vacuum heat-insulating plate possesses: the inorfil congeries that will not comprise tackiness agent is contained in the core in the inner bag that is made of monomer or plastic pellicle; And the outsourcing material that constitutes by laminated film that holds above-mentioned core, reduced pressure and periphery is carried out deposited sealing in inside.
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| JP5753732B2 (en) * | 2011-05-13 | 2015-07-22 | 日立アプライアンス株式会社 | Heat insulation box |
| CN102775573A (en) * | 2011-05-13 | 2012-11-14 | 日立空调·家用电器株式会社 | Adiabatic housing |
| WO2013146286A1 (en) * | 2012-03-26 | 2013-10-03 | 三菱電機株式会社 | Heat insulating box, and refrigerator and hot-water storage device each comprising heat insulating box |
| KR101444530B1 (en) * | 2012-04-23 | 2014-10-30 | 히타치 어플라이언스 가부시키가이샤 | Insulation door and insulation box structure |
| CN103374113B (en) * | 2012-04-23 | 2015-10-07 | 日立空调·家用电器株式会社 | Hard polyurethane foam and the many alcohol of hard polyurethane foam manufacture pre-mixing |
| CN103983064B (en) * | 2014-05-16 | 2016-04-13 | 苏州安特实业有限公司 | Passive car refrigerator |
| CN104890167A (en) * | 2015-05-28 | 2015-09-09 | 南京皓威机械有限公司 | Thermal insulating pipeline casting mould |
| WO2021058774A1 (en) * | 2019-09-27 | 2021-04-01 | Basf Se | Foam separator for polyurethane foams |
| CN113459378B (en) * | 2020-03-30 | 2022-12-16 | 青岛海尔电冰箱有限公司 | Ice thermal insulation box body, preparation method thereof and refrigerator with same |
| CN115091681A (en) * | 2020-05-23 | 2022-09-23 | 侯奥 | Multifunctional foaming mold system and using method thereof |
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| JP3475763B2 (en) * | 1998-01-09 | 2003-12-08 | 株式会社日立製作所 | Insulated box for refrigerator |
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