CN100516626C - Vacuum heat-insulating board and instrument with the same - Google Patents
Vacuum heat-insulating board and instrument with the same Download PDFInfo
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- CN100516626C CN100516626C CNB2007101403461A CN200710140346A CN100516626C CN 100516626 C CN100516626 C CN 100516626C CN B2007101403461 A CNB2007101403461 A CN B2007101403461A CN 200710140346 A CN200710140346 A CN 200710140346A CN 100516626 C CN100516626 C CN 100516626C
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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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- Thermal Insulation (AREA)
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Details Of Fluid Heaters (AREA)
- Electric Ovens (AREA)
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Abstract
The present invention provides a high-performance vacuum insulation panel which can restrain the deterioration of the thermal conductivity along with the time and has the advantages of transpiercing-proofing, rupture-proofing, high strength, low cost and using in the hot environment. In the vacuum insulation panel the glass mineral wool which has an average fiber diameter from 3 to 5 mu m and comprises no adhesive and the getter are covered by the sheathing material that is composed of metal foil, the organic polymers (polyimide, polyamideimide, polymidesiloxane, polyamide) which have an excellent oxygen transmissivity are used to fused to joint the sheathing material to realize the pressure and seal the inner side. The fusing layer only form the frame-shape fusing-jointing part and can hold the adhesive strength and restrain the generating of the emergent gas. The vacuum insulation panel is arranged in the device comprising at least a heating component with 150 DEG C at the part which should be heat insulated.
Description
Technical field
The present invention relates to block the vacuum heat-insulating plate of heat affecting, relate in particular to vacuum heat-insulating plate, its manufacture method that is used for high-temperature part heater etc. and the utensil that uses this vacuum heat-insulating plate.
Background technique
In recent years, in order to tackle global warming,, wish to reduce the consumption of power consumption homenergic for the various products that comprise household electrical appliances.For example, the power consumption of refrigerator is if the carrying capacity in the refrigerator is certain, by improving the heat-insulating property of cooling with the efficient of compressor and the thermoinsulation material relevant with the heat leak amount, the just energy that can reduce to consume.
Before this, people have developed the high-performance vacuum heat-insulating plate that reduces pyroconductivity, are used for refrigerated warehouse and freezer etc. mostly.Especially vacuum heat-insulating plate is compared with thermoinsulation materials such as polyurethane foams, and its pyroconductivity is very superior.The structure of vacuum heat-insulating plate is to embed the core material as core, the getter of absorption emergent gas in sheathing material, thereby make inner pressure relief.The sheathing material that uses is the cheap organic film that adopts universal product at present, by preparing with the bonding layered manner of binder on whole of barrier layer for gases.As barrier layer for gases, be that aluminium foil, aluminium-vapour deposition film, isovaline phenolphthalein film, polyester film etc. are compound, the nylon film of on protective layer, fitting.The welding layer uses polyethylene film or polypropylene film.
Around the high-temperature component of high-frequency electronic food heater, heating cooker, thermostat, duplicating machine, laser printer, vehicle etc., also wish to use vacuum heat-insulating plate, thereby need exploitation have stable on heating Vacuum thermal insulating material.
In order to improve heat resistance, must make heat-resistingization of sheathing material.As commercially available high temperature sheathing material, in alembic food, be the laminate film that in hot welding layer, uses Noblen (CPP).It is that about 120 ℃ spy opens 2004-332929 communique (patent documentation 1) that hot welding layer is used the heat resisting temperature of the sheathing material of CPP floor; put down in writing comprise have hot welding layer, the Vacuum thermal insulating material of the stacked sheathing material of barrier layer for gases, protective layer; wherein, use the high film of fusing point as hot welding layer.
Open in the 2005-114013 communique (patent documentation 2) the spy, put down in writing the self-extinguish ability film that has flame retarding at the outermost surface of thermoinsulation material.
The spy opens in the 2005-114014 communique (patent documentation 3), put down in writing adhesive layer and be acrylic acid, polyester, epoxy resin, polysiloxane-based tackiness agent.
The spy opens in the 2001-141179 communique (patent documentation 4), has put down in writing the Vacuum thermal insulating material of barrier layer for gases use metal.
Patent documentation 1: the spy opens the 2004-332929 communique
Patent documentation 2: the spy opens the 2005-114013 communique
Patent documentation 3: the spy opens the 2005-114014 communique
Patent documentation 4: the spy opens the 2001-141179 communique
Summary of the invention
For example the thermal shield that uses in baking box and the cooking heater etc. requires the heat resistance more than at least 150 ℃.Yet, heat resistance height, low-cost Vacuum thermal insulating material also can't be provided at present.
The vacuum heat-insulating plate of record is to constitute by heat-pesistant thin film is stacked in the patent documentation 1～4, owing to produce emergent gas under hot environment, the pyroconductivity of vacuum heat-insulating plate improves.In addition, heat-pesistant thin film is very expensive, so the cost of sheathing material increases.
In addition,, the method with metal solder such as the ironed films of aluminium lamination is arranged, yet this method is difficult to form for example size of 200 * 1500mm as the high temperature sheathing material.This be because, the metal foil thickening of sheathing material, pyroconductivity improves, perhaps sheathing material increases, parallel when being difficult to keep welding.
In addition, the hot welding layer of the fluorine class film of fusing point more than 200 ℃, though heat resistance and excellent in flame retardance, (at wrapping angle is under 100～115 degree but owing to non-adhesiveness, can't bond as sealing material), therefore, if be used for the hot welding layer of sheathing material, then bonding strength reduces, and possibly can't keep insulation effect.
Therefore, the objective of the invention is, a kind of cheap, vacuum heat-insulating plate that insulation effect is high is provided.
The present invention who solves above-mentioned the application's problem is a kind of vacuum heat-insulating plate, it is characterized in that, have: the pair of metal paper tinsel, form between the above-mentioned metal foil or be arranged to have the welding layer of the shape of one or more opening portions, overlapping setting and do not contain the inorfil core of tackiness agent and the getter of adsorbed gas composition on above-mentioned opening portion, cover reduced pressure sealing behind above-mentioned core and the getter with above-mentioned metal foil.
Above-mentioned welding layer forms the frame shape in the edge section of the metal foil of carrying out welding.Compare with the situation that was attached to the front in the past, can reduce the thickness of vacuum heat-insulating plate, and can reduce cost.In addition, can also on a metal foil, form the frame shape welding layer that a plurality of openings are set, core etc. is set respectively therein, thereby form the vacuum heat-insulating plate that inside is cut into a plurality of zones.
The welding layer uses the low organic polymer of oxygen permeability.Described organic polymer is especially preferentially selected at least a in polyimide, polyamidoimide, Polyimidesiloxane, the polyamide resin for use.In addition, using varnish to form the occasion of welding layer, preferably finish the organic polymer reaction in the stage of varnish coating.
Above-mentioned core, preferred average fiber directly is the glass wool of 3～5 μ m.This be because, if fiber diameter is excessive, then pyroconductivity increases, if fiber diameter is too small, inconvenient operation then.In addition, core does not contain jointing materials such as tackiness agent.This is for fear of by emergent gas in the tackiness agent, causes pyroconductivity to improve.
The preferred alloy foil of metal foil, stainless steel foil.Compare with the aluminium foil of frequent use, can reduce pyroconductivity.As for thickness, for stainless steel foil, paper tinsel is thick can 20～100 μ m, for alloy foil, can be 15～30 μ m.According to the present invention, use than thick slightly in the past metal foil also to be fine.
Laminated film also can be used in combination with aluminium foil, for the present invention, also is no problem though carry out lamination process equally, not necessarily.Remove laminated film, can reduce manufacturing process and reduce production costs.
Adopt the scheme of above-mentioned formation, can provide can under high temperature condition, use, adiabaticity is high and low-cost vacuum heat-insulating plate.
In addition, in various goods with high-temperature part, use thermal shield of the present invention, can reduce energy consumption.Particularly, can reduce the electric weight of consumption in device or the inner heat affectings of blocking about at least 150 ℃ high temperature heating part of device such as thermostat, baking box or IH cooking heaters.
Brief description of drawings
Fig. 1 (a) is the structural drawing of vacuum heat-insulating plate in the past, (b) is the sheathing material of vacuum heat-insulating plate in the past and the sectional schematic diagram of weld.
Fig. 2 (a) is the structural drawing of vacuum heat-insulating plate of the present invention, (b) is the sheathing material of vacuum heat-insulating plate of the present invention and the sectional schematic diagram of weld, (c) is the oblique drawing that welding layer of the present invention forms part.
Fig. 3 is the sectional schematic diagram that has inserted the thermostatic bath of vacuum heat-insulating plate of the present invention.
Fig. 4 is the sectional schematic diagram that has inserted the baking box of vacuum heat-insulating plate of the present invention.
Fig. 5 is the sectional schematic diagram that has inserted the IH cooking heater of vacuum heat-insulating plate of the present invention.
Symbol description
1... vacuum heat-insulating plate in the past, 2... core, 3... getter, 4,7... sheathing material, 4-1... pet film, 4-2... nylon film, 4-3... aluminium foil, 5,8... weld, 6... vacuum heat-insulating plate of the present invention, 9... metal foil, 10... thermostatic bath door, 11... dividing plate, the 12... thermostatic bath interior space, the 13... baking box interior space, 14... oven door, 15... top board, 16... indcution heater, 17... grill door, 18... grill glass, 19... grill handle, 20... control circuit.
Embodiment
With reference to accompanying drawing, structure and the preparation with the device that inserts this vacuum heat-insulating plate describes to vacuum heat-insulating plate of the present invention.The structure of Fig. 1 (a) expression vacuum heat-insulating plate in the past, the sectional schematic diagram of Fig. 1 (b) expression case member and weld.Utilize sheathing material 4 and weld 5 with the core 2 of inorfil and getter 3 reduced pressure sealings in vacuum heat-insulating plate 1, constitute vacuum heat-insulating plate.Fig. 2 (a) is the structure of vacuum heat-insulating plate of the present invention, the sectional schematic diagram of Fig. 2 (b) expression sheathing material and weld.Utilize sheathing material 7 and weld 8 will not contain the inorfil core 2 of tackiness agent and getter 3 reduced pressure sealings in vacuum heat-insulating plate 6, constitute vacuum heat-insulating plate.In addition, on metal foil 9, form the welding layer formation oblique drawing partly of the weld 8 of frame shape shown in Fig. 2 (c).
Formed the frame shape as the welding layer, preferable width is about 10～30mm, and thickness is about 10～50 μ m.Between welding layer and sheathing material, the layer that can also set in advance the layer that improves cementability or improve sheathing material intensity waits the layer of other purpose.Adopt said structure, do not need to resemble the preparation method of sheathing material in the past the heat-pesistant thin film of stacked high price on whole, cost has reduced.In addition, because the bonding strength excellence can suppress the generation of emergent gas, therefore can improve heat resistance.
Use covers inorfil core and the getter that does not contain tackiness agent by the sheathing material that metal foil constitutes, and will seal after the inner pressure relief, forms vacuum heat-insulating plate.Especially in the edge section of sheathing material, the organic polymer that uses the frame shape is as the welding layer.Have only sealing layer to use the organic polymer of OTR oxygen transmission rate excellence, just can prevent that all gases from seeing through.In addition, can also suppress to select gas, suppress the deterioration of continuity in time.In addition, can also further reduce cost.
The welding layer uses the little organic polymer of OTR oxygen transmission rate.The preferred oxygen vapor permeability is 500cc/m
2Organic polymer below day.Here said OTR oxygen transmission rate is H
2O, CO
2, O
2Gas etc. see through index.As the welding layer, preferably use at least a in polyimide, polyamidoimide, Polyimidesiloxane, the polyamide resin.These resins are thermosetting resins, therefore do not have softening temperature, are fit at high temperature use.In addition, especially preferably using glass transition temperature is 160～230 ℃ organic polymer.Use the lower organic polymers such as polyimide of glass transition temperature, even under about 200 ℃ low temperature, hot-pressing is also carried out easily.
Adopt such formation scheme, can obtain the vacuum heat-insulating plate that deterioration is less, heat resistance is high under the high temperature.In addition, bonding strength strengthens.
Wherein, polyimide, polyamidoimide, Polyimidesiloxane, polyamide can be dissolved in solvent, form varnish.Solvent can use N-N-methyl-2-2-pyrrolidone N-, dimethylacetylamide, dimethyl formamide, methyl-sulfoxide, sulfolane, benzyl alcohol ether, tetrahydrofuran, diox, butyrolactone etc.
The varnish of polyimide etc. can be by adding roughly equimolar raw material, for example two amine components and sour composition and directly synthesize in solvent.
Below, in example, polyimide resin is described.Usually, polyimide is to come two amine components and the reaction of sour composition synthetic.If polyimide resin reacts near room temperature, can obtain polyimide precursor varnish, if near reaction 180 ℃, could synthesis of polyimides varnish.
Usually use polyimide resin, for example in the flexible print wiring board of copper foil layer laminated substrate, semiconductor passivation etc., use the occasion of polyimide, can use the polyimide of polyimide precursor type, formation film the back under the high temperature more than 250 ℃ the thermal dehydration closed loop.
Yet, as the vacuum insulation that uses among the application sheathing material sealing layer, compare with polyimide precursor, preferentially select polyimide varnish for use.This is because if the hot welding layer of sheathing material is used polyimide precursor varnish, the dehydration closed-loop during then owing to imidizate can produce the emergent gas of water, thereby must increase the consumption of getter.In addition, owing to carry out hot-pressing when sealing under the temperature about 200 ℃, compare the bonding strength deterioration with the occasion of direct polyimide varnish.
Resins such as the polyimide that uses among the present invention can preferably be finished imidizate in the stage of varnish by 1 step of raw material direct synthetic varnish (reaction liquid), form the varnish of excellent storage stability.
Two amine components that are used for synthesis of polyimides, for example can enumerate: 3,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 3,3 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 3,3 '-diamino-diphenyl propane, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [3-(3-amino-benzene oxygen) phenyl] sulfone, 1,7-diaminourea heptane, 1, the 6-diamino hexane, 4,4 '-di-2-ethylhexylphosphine oxide (2-methyl cyclohexane alkanamine), isophthalic dihydrazide, sebacic dihydrazide, the amber acid dihydrazide, two (3-aminopropyl) tetramethyl disiloxane, 1,1,3,3-four benzyls-1,3-two (4-aminophenyl) disiloxane, 1,1,3,3-four phenoxy groups-1,3-two (4-amino-ethyl) disiloxane etc.
Be used for the sour composition of synthesis of polyimides, for example can use dicyclo (2,2,2) suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic dianhydride, m-phthaloyl chloride, stearyl chloride etc. are synthetic.
The bonding strength of welding layer under 150 ℃ gets final product more than 10N/15mm.Even because under hot environment, the bonding strength of sealing weld is also fine, and pyroconductivity is difficult for deterioration in time.The durability of vacuum heat-insulating plate is improved.In addition, bonding strength is to film etc. by form organic macromolecule on stainless steel foil or alloy foil, and 90 ° peeling force using electronic tension tester (Tensilon) to estimate is confirmed.
Inorganic fibers is preferentially selected glass wool for use.The fiber diameter that depends on glass wool, pyroconductivity and cost have a great difference.The glass wool cost that fiber diameter is big is low, thereby preferentially selects for use.In addition, the thickness of core is easy to generate, and it is also easy to operate.In addition, the glass wool that the average fiber footpath is little is because fiber is difficult to arrange on same direction, and therefore big the thereby pyroconductivity reduction of thermal contact resistance is preferred.
In the present invention, inorfil especially preferably has the fiber of 3～5 μ m fiber diameter.The fiber hot-fluid road of this fiber diameter is a zigzag, can also increase thermal resistance except that thermal contact resistance, reduces pyroconductivity.
Inorganic fibers does not preferably contain jointing material, and this is because meeting produces emergent gas in the jointing material, for the maintaining heat conductivity, must increase the amount of getter.
As mentioned above, in order to adsorb internal gas, reduce pyroconductivity, getter must be sealed with core, purpose is to improve the reliability of vacuum heat-insulating plate.As required, getter preferably uses moisture adsorbent such as adsorbent such as the double salt (dowsonite), hydrotalcite (hydrotalcite), metal hydroxides of aluminium hydroxide and sodium carbonate or molecular sieve, silica gel, calcium oxide, zeolite, active carbon, caustic potoash, sodium hydroxide, lithium hydroxide etc., perhaps their is mixed and uses.
Metal foil also can be used than thick slightly in the past metal foil.Like this, can resist and pierce through, split, the realization high strength also reduces cost.In preferred especially stainless steel foil or the alloy foil any.Except pyroconductivity, consider that from the angle of intensity and operability stainless steel foil thickness can be 20～100 μ m, the thickness of alloy foil can be 15～30 μ m.
In addition, can also and conduct the less metal of heat of inflow along metal foil with iron, nickel, tin, titanium, carbon steel etc.In addition, can also and use metal evaporation things such as aluminium, cobalt, nickel, zinc.
Method for making to the welding layer has no particular limits, and applying of dipping body such as applying that can be by suitable solution coat film, film, nonwovens etc. is carried out.
The solution coat film adopts method manufacturings such as silk-screen printing, roller coat.At glass substrate top pouring varnish, after 90 ℃ of following dryings, it is peeled off promptly and obtain to film.The dipping body of nonwovens etc. is the reinforcing material dipping solution that will be made of reinforced fiber, uses as prepreg (pre-preg).Reinforcing material can use sheet, nonwovens shape, fibrous material.When especially using glass fibre, pyroconductivity is less, thereby is preferred.
The welding of welding layer, sealing can be undertaken by hot-pressing.The method of hot-pressing has no particular limits, and needs only fixedly welding layer, for example can enumerate hot pressing, hot rolling etc.If adopt the vacuum pressing method, can under decompression state, heat and pressurize, preparation does not have the sheathing material of defective.
Vacuum heat-insulating plate of the present invention, being suitable for household electric appliance or building materials etc. needs adiabatic position.Be particularly preferred for baking box, cooking stove, cooking heater, burn the insulation position of the high-temperature part of soup device etc., perhaps the position that high-temperature part and low temperature partly must be separated.
For example, can enumerate refrigerator, air conditioner outdoor machine etc., can enumerate around wall material, the bathroom, can enumerate vehicle and medical checking apparatus, thermostatic containers etc. such as automobile, train in addition as building materials as household electric appliance.In addition, the present invention is not limited to have in the goods etc. of the heating part more than 150 ℃ of high temperature, even using below 150 ℃, durability is also fine, can keep thermal insulation, is preferred therefore.
In addition, preferred maximum temperature is position following about 220 ℃, this be because, promote organic macromolecule welding layer deterioration or rotten sometimes, can't keep cementability.
Fig. 3 represents to insert the schematic cross-section of the thermostatic bath of vacuum heat-insulating plate 6 of the present invention, is the example that the periphery in the door 10 of thermostatic bath and the interior space 12 uses.
Fig. 4 represents the schematic cross-section of baking box, is the example that inserts vacuum heat-insulating plate 6 of the present invention in the door 14 and the inboard of the interior space 13 of baking box.
Fig. 5 represents the schematic cross-section of IH cooking heater.Vacuum heat-insulating plate 6 of the present invention is inserted at the position around the grill of IH cooking heater.
Embodiment
Below, by embodiment polyimide, polyamidoimide, Polyimidesiloxane, polyamide and the synthetic method of using among the present invention, the preparation of vacuum heat-insulating plate and the evaluation of pyroconductivity, the device that uses this thermal shield etc. are elaborated.The core that uses in the vacuum heat-insulating plate shown in the table 1, sheathing material, welding layer, oxygen permeability, glass transition temperature, bonding strength, initial stage pyroconductivity, continue pyroconductivity after the deterioration in time.In addition, the present invention is not subjected to these embodiments to carry out any restriction.
In an embodiment, adopt following method to carry out the mensuration of oxygen permeability, bonding strength, glass transition temperature.
＜oxygen permeability 〉
The varnish curtain coating to glass substrate, is peeled off after 90 ℃ of following dryings, 230 ℃ of following heat treated, obtained film again.The gained film is cut into width and length is the 100mm size, (MOCON company makes, model: OX-TRAN2/21), carry out oxygen permeability mensuration under 25 ℃ of temperature, drying, 24 hours condition to use the oxygen permeability testing apparatus.
＜bonding strength 〉
The sample film of mounting width 15mm is fixed on the hotpress on stainless steel foil, starts hotpress, with 0.3～1.0kgf/cm
2About pressure, 200 ℃ of down pressurizations 5～30 minutes, cooling uses resulting sample to carry out the mensuration of 90 ° of peeling forces then.Mensuration is carried out according to JIS C6481, the Tensilon MPW-300S that testing machine uses オ リ エ Application テ Star Network company to make.
＜glass transition temperature 〉
The thermo-mechanical analysis device TMA that uses Seiko Electronics Industry Company to make, one side uses the cylinder quartz probe to apply load on the film of test preparation, and one side is under the condition of 10 ℃/minute of warming velocitys, measure in the scope of room temperature～300 ℃.
Embodiment 1
Embodiment 1 is to use 176 ℃ of glass transition temperatures, oxygen permeability 390cc/m
2It polyimide is as the example of the vacuum heat-insulating plate of welding layer.
Synthesizing of＜polyimide melted material 1 〉
In being installed, the separable flask of stirrer forms reaction tank, described reaction tank has been installed the cooling tube that coagulates air valve with the cock of band silicone rubber, in this reaction tank, as raw material, add 9.9g dicyclo (2,2,2) suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 12.0g 3,4 '-diamino-diphenyl ether, 200g N-N-methyl-2-2-pyrrolidone N-and 30g toluene stirred 10 minutes at normal temperatures with in the blanket of nitrogen, and the content with reaction tank is warming up to 180 ℃ then, with the speed setting of stirrer is 180rpm, reacts 1 hour.Then, with the reaction liquid air cooling, add 14.7g 3 again, 3 ', 4,4 '-diphenyl tetracarboxylic dianhydride, 16.1g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 10.4g 1,7-diaminourea heptane, 160g N-N-methyl-2-2-pyrrolidone N-and 30g toluene are warming up to 180 ℃ of stirring reactions that carry out 2 hours once more.Therebetween, the rotating speed of stirrer is 180rpm, and the water of generation is by discharging in the silicon cock, thereby has synthesized polyimide varnish.
In addition, the occasion of using after the purity that improves varnish is injected excessive methyl alcohol with gained reaction liquid (varnish), stirs with mixer toner is separated out.With this powder of methanol cleaning, dry at normal temperatures, then at about 150 ℃ of following drying under reduced pressure, obtain highly purified polyimide varnish by being dissolved in again to use in the N-N-methyl-2-2-pyrrolidone N-.
The TSK gel GMH-M type gel column and the UV-8020 type detector that use eastern ソ-company to make, the weight average molecular weight (Mw) of mensuration varnish, result, weight average molecular weight are 42000, resinous principle content is 23.2 weight %.In addition, prepare the film of about 25 μ m, measure its physics value, result, oxygen permeability 390cc/m
2My god, glass transition temperature is 176 ℃, the bonding strength under 150 ℃ of temperature is 13.8N/15mm.
The vacuum heat-insulating plate embodiment's 1 of＜use polyimide melted material 1 preparation 〉
Synthetic polyimide melted material 1 is used for the sealing layer of sheathing material, preparation vacuum heat-insulating plate example 1.
For the stainless steel foil of the about 30 μ m of thickness, use screen process press, be coated with the thick above-mentioned synthetic polyimide varnish of about 30 μ m in its edge section with the shape of frame shape.Under 70～90 ℃, make the semi-solid preparation of filming, a pair of stainless steel foil is arranged in the hotpress, under about 200 ℃ temperature, apply 0.83kg/cm
2Pressure, preparation is with the sheathing material of the airtight sealing of three parts.
As the core of vacuum heat-insulating plate, use the glass wool that to carry out 1 hour burn into fiber diameter under 180 ℃ be 3 μ m.In the bag shape sheathing material of semi-solid preparation, pack into the getter (molecular sieve 13X/ active carbon) of core glass wool and adsorbed gas.
At final sealed department office coating polyimide, the rotary pump exhaust of usefulness vacuum package machine 10 minutes was used the diffusion pump exhaust 10 minutes again, made the internal pressure of vacuum heat-insulating plate reach 1.3Pa.Then, by heat-sealing end seal is lived.
Measure the vacuum heat-insulating plate example 1 (thickness: pyroconductivity about 8mm) that obtains thus.Use AUTO-A that the great smart machine (strain) of English makes, under 10 ℃ condition, the initial stage pyroconductivity is 4.1mW/mK.Carry out 1 month deterioration test under 160 ℃, the pyroconductivity after the deterioration test is 5.2mW/mK.As mentioned above, even vacuum heat-insulating plate of the present invention can not continue in time under hot environment yet and worsen, can the maintaining heat conductivity.
In addition, polyimide is a thermosetting resin, does not at high temperature also have softening point, therefore also can keep cementability under the high temperature about 70～80 ℃ more than the glass transition temperature, therefore, estimate that vacuum heat-insulating plate embodiment 1 can use under 240～260 ℃ of left and right sides temperature.
＜use vacuum heat-insulating plate embodiment 1 thermostatic bath example 〉
Because at high temperature the peripheral part of the thermostatic bath that uses and the door back side are high temperature, therefore can't lay existing vacuum heat-insulating plate.Above-mentioned vacuum heat-insulating plate embodiment 1 can be inserted the peripheral part and the door back side of thermostatic bath uses.
Compare with the situation that vacuum heat-insulating plate is not set, consumes power has reduced about 5%.In addition, can keep insulation effect for a long time.In addition, compare, use vacuum heat-insulating plate can reduce the thickness of heat insulation layer, can enlarge the interior space with respect to the volume that installs with thermal shield in the past.
Synthesizing of＜polyimide melted material 2 〉
In the separable flask of stirrer has been installed, constitute the reaction tank that cooling tube has been installed, described cooling tube has the condenser valve of band silicone rubber cock, in this reaction tank, as raw material, add 9.9g dicyclo (2,2,2) suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 12.0g 3,4 '-diamino-diphenyl ether, 200gN-N-methyl-2-2-pyrrolidone N-and 30g toluene, stirred 10 minutes at normal temperatures with in the nitrogen atmosphere, then the content in the reaction tank being warming up to 180 ℃, is 180rpm with the speed setting of stirrer, reacts 1 hour.Then, with the reaction liquid air cooling, add 14.7g 3 again, 3 ', 4,4 '-diphenyl tetracarboxylic dianhydride, 16.1g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 19.1g 4,4 '-di-2-ethylhexylphosphine oxide (2-methyl cyclohexane alkanamine), 160g N-N-methyl-2-2-pyrrolidone N-and 30g toluene are warming up to 180 ℃ of stirring reactions that carry out 1.5 hours once more.Therebetween, the rotating speed of stirrer is 180rpm, and the water that generates is discharged from the silicone rubber cock, has synthesized polyimide varnish.
The weight average molecular weight of varnish is 62000, and resinous principle content is 20 weight %.In addition, prepare the film of about 25 μ m, measure its physics value, the result, oxygen permeability is 420cc/m
2My god, glass transition temperature is 226 ℃, the bonding strength under 150 ℃ of temperature is 15.1N/15mm.
The vacuum heat-insulating plate embodiment's 2 of＜use polyimide melted material 2 preparation 〉
Synthetic polyimide melted material 2 is used for the sealing layer of sheathing material, use fiber diameter be the glass wool of 3.5 μ m as core, in addition, operate equally with vacuum heat-insulating plate example 1, prepare vacuum heat-insulating plate example 2.
The vacuum heat-insulating plate example 2 that obtains like this (thickness: pyroconductivity about 8mm), measure equally with thermal shield example 1, under 10 ℃ condition, the initial stage pyroconductivity is 4.1mW/mK, the pyroconductivity after carrying out 1 month deterioration test under 200 ℃ is 5.9mW/mK.As mentioned above, even vacuum heat-insulating plate of the present invention can not continue in time under hot environment yet and worsen, can the maintaining heat conductivity.
Similarly to Example 1, also can keep cementability under the high temperature about 70～80 ℃ more than the glass transition temperature, therefore, vacuum heat-insulating plate embodiment 2 estimates also can use down about 280 ℃.
＜use vacuum heat-insulating plate embodiment 2 baking box example 〉
Above-mentioned vacuum heat-insulating plate embodiment 2 is inserted at the peripheral part and the door back side at baking box, observes its effect.Same with thermostatic bath, baking box is a high temperature, can't lay vacuum heat-insulating plate in the past.
Compare with the situation that vacuum heat-insulating plate is not set, consumes power has reduced about 3%.In addition, insulation effect can keep for a long time.In addition, compare, use vacuum heat-insulating plate can reduce the thickness of heat insulation layer, enlarge the interior space with respect to the volume that installs with thermal shield in the past.
Embodiment 3
Embodiment 3 uses 161 ℃ of glass transition temperatures, oxygen permeability 390cc/m
2It polyimide is as the example of the vacuum heat-insulating plate of welding layer.
Synthesizing of＜polyimide melted material 3 〉
In the separable flask of stirrer has been installed, installation has the cooling tube of the condenser valve of band silicone rubber cock, constitute reaction tank, in this reaction tank, as raw material, add 9.9g dicyclo (2,2,2) suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 4g 3,4 '-diamino-diphenyl ether, 5.2g 1,7-diaminourea heptane, 200g N-N-methyl-2-2-pyrrolidone N-and 30g toluene stirred 10 minutes at normal temperatures with in the blanket of nitrogen, and the content with reaction tank is warming up to 180 ℃ then, with the speed setting of stirrer is 180rpm, reacts 1 hour.Then, with the reaction liquid air cooling, add 14.7g 3 again, 3 ', 4,4 '-diphenyl tetracarboxylic dianhydride, 16.1g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 10.4g 1,7-diaminourea heptane, 160g N-N-methyl-2-2-pyrrolidone N-and 30g toluene are warming up to 180 ℃ of stirring reactions that carry out 2.0 hours once more.Therebetween, the rotating speed of stirrer is 180rpm, and the water that generates is discharged from the silicone rubber cock, has synthesized polyimide varnish.
The weight average molecular weight of varnish is 25000, and resinous principle content is 20 weight %.In addition, prepare the film of about 25 μ m, measure its physics value, the result, oxygen permeability is 390cc/m
2My god, glass transition temperature is 161 ℃, the bonding strength under 150 ℃ of temperature is 12.5N/15mm.
The vacuum heat-insulating plate embodiment's 3 of＜use polyimide melted material 3 preparation 〉
Synthetic polyimide melted material 3 is used for the sealing layer of sheathing material, and in addition the glass wool that uses fiber diameter 4.5 μ m operate with vacuum heat-insulating plate example 1 equally as core, prepares vacuum heat-insulating plate example 3.
The vacuum heat-insulating plate example 3 that obtains like this (thickness: measure equally, and under 10 ℃ condition, the initial stage pyroconductivity is 4.3mW/mK by pyroconductivity about 8mm) and thermal shield example 1.Pyroconductivity after carrying out 1 month deterioration test under 150 ℃ is 5.5mW/mK.As mentioned above, even vacuum heat-insulating plate of the present invention can not worsen under hot environment in time yet, can the maintaining heat conductivity.
Similarly to Example 1, also can keep cementability under the high temperature about 70～80 ℃ more than the glass transition temperature, therefore, vacuum heat-insulating plate embodiment 3 estimates also ability use under 230～240 ℃.
The cooking heater example of＜use vacuum heat-insulating plate 3 〉
In the grill peripheral part of IH cooking heater, use above-mentioned vacuum heat-insulating plate embodiment 3, observe its effect.Same with thermostatic bath, be high temperature in the cooking heater, can't lay existing vacuum heat-insulating plate.
By with the thermal insulation of grill wall, can get rid of heat affecting to control circuit.In addition, compare with the situation that vacuum heat-insulating plate is not set, consumes power has reduced about 5%.In addition, can the long term maintenance insulation effect.
Can expect that by the foregoing description using it for equally to need the part of low temperature and the goods of high-temperature part thermal insulation to control circuit etc., for example is used for automobile etc., also can obtain same effect.
Embodiment 4
Embodiment 4 is to use 170 ℃ of glass transition temperatures, oxygen permeability 450cc/m
2It polyamidoimide is as the example of the vacuum heat-insulating plate of welding layer.
Synthesizing of＜polyamidoimide melted material 4 〉
In the separable flask of stirrer has been installed, constitute the reaction tank that cooling tube has been installed, described cooling tube has the condenser valve of band silicone rubber cock, in this reaction tank, as raw material, add 9.9g dicyclo (2,2,2) suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 4g 3,4 '-diamino-diphenyl ether, 200g N-N-methyl-2-2-pyrrolidone N-and 30g toluene.Stirred 10 minutes at normal temperatures with in the blanket of nitrogen, the content with reaction tank is warming up to 180 ℃ then, and the speed setting of stirrer is 180rpm, reacts 1 hour.Then, with the reaction liquid air cooling, add 14.7g 3 again, 3 ', 4,4 '-diphenyl tetracarboxylic dianhydride, 16.1g 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 15.5g isophthalic dihydrazide, 160g N-N-methyl-2-2-pyrrolidone N-and 30g toluene are warming up to 180 ℃ of stirring reactions that carry out 2.5 hours once more.Therebetween, the rotating speed of stirrer is 180rpm, and the water that generates is discharged from the silicone rubber cock, has synthesized polyamidoimide varnish.
The weight average molecular weight of varnish is 45000, and resinous principle content is 23.4 weight %.In addition, prepare the film of about 25 μ m, measure its physics value, the result, oxygen permeability is 450cc/m
2My god, glass transition temperature is 170 ℃, the bonding strength under 150 ℃ of temperature is 12.8N/15mm.
The vacuum heat-insulating plate embodiment's 4 of＜use polyamidoimide melted material 4 preparation 〉
Synthetic polyamidoimide melted material 4 is used for the sealing layer of sheathing material, in addition operate equally, prepare vacuum heat-insulating plate example 4 with vacuum heat-insulating plate example 1.
The vacuum heat-insulating plate example 4 that obtains like this (thickness: measure equally, and under 10 ℃ condition, the initial stage pyroconductivity is 4.2mW/mK, and the pyroconductivity after carrying out 1 month deterioration test under 160 ℃ is 5.3mW/mK by pyroconductivity about 5mm) and thermal shield example 1.As mentioned above, even vacuum heat-insulating plate of the present invention can not worsen under hot environment in time yet, can the maintaining heat conductivity.
Similarly to Example 1, polyamidoimide also is a thermosetting resin, also can keep cementability under the high temperature about 70～80 ℃ more than the glass transition temperature, and therefore, vacuum heat-insulating plate embodiment 4 estimates and can also can anti-ly use under 230～250 ℃.
Embodiment 5
Embodiment 5 is to use 165 ℃ of glass transition temperatures, oxygen permeability 400cc/m
2It Polyimidesiloxane is as the example of the vacuum heat-insulating plate of welding layer.
Synthesizing of＜Polyimidesiloxane melted material 5 〉
In the separable flask of stirrer has been installed, constitute the reaction tank that cooling tube has been installed, described cooling tube has the condenser valve of band silicone rubber cock, in this reaction tank, as raw material, add 9.9g dicyclo (2,2,2) suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 4g 3,4 '-diamino-diphenyl ether, 200g N-N-methyl-2-2-pyrrolidone N-and 30g toluene.Stirred 10 minutes at normal temperatures with in the blanket of nitrogen, the content with reaction tank is warming up to 180 ℃ then, and the speed setting of stirrer is 180rpm, reacts 1 hour.Then, with the reaction liquid air cooling, add 14.7g 3 again, 3 ', 4,4 '-diphenyl tetracarboxylic dianhydride, 16.1g3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, two (3-aminopropyl) tetramethyl disiloxanes of 19.8g, 160gN-N-methyl-2-2-pyrrolidone N-and 30g toluene are warming up to 180 ℃ of stirring reactions that carry out 3.5 hours once more.Therebetween, the rotating speed of stirrer is 180rpm, and the water that generates is discharged from the silicone rubber cock, has synthesized Polyimidesiloxane varnish.
The weight average molecular weight of varnish is 21000, and resinous principle content is 21.3 weight %.In addition, prepare the film of about 25 μ m, measure its physics value, the result, oxygen permeability is 400cc/m
2My god, glass transition temperature is 165 ℃, the bonding strength under 150 ℃ of temperature is 12.9N/15mm.
The vacuum heat-insulating plate embodiment's 5 of＜use Polyimidesiloxane melted material 5 preparation 〉
Synthetic Polyimidesiloxane melted material 5 is used for the sealing layer of sheathing material, and coating varnish reaches 40 μ m, in addition operate equally with vacuum heat-insulating plate example 1, prepares vacuum heat-insulating plate example 5.
The vacuum heat-insulating plate example 5 that obtains like this (thickness: measure equally, and under 10 ℃ condition, the initial stage pyroconductivity is 4.1mW/mK, and the pyroconductivity after carrying out 1 month deterioration test under 150 ℃ is 5.3mW/mK by pyroconductivity about 10mm) and thermal shield example 1.As mentioned above, even vacuum heat-insulating plate of the present invention can not worsen under hot environment in time yet, can the maintaining heat conductivity.
Similarly to Example 1, the Polyimidesiloxane resin also is a thermosetting resin, also can keep cementability under the high temperature about 70～80 ℃ more than the glass transition temperature, therefore, vacuum heat-insulating plate embodiment 5 estimates also can anti-ly to use under 230～250 ℃.
Synthesizing of＜polyamide melted material 6 〉
In the separable flask of stirrer has been installed,, add 8.1g m-phthaloyl chloride, 12.0g 3,4 '-diamino-diphenyl ether, 200g N-N-methyl-2-2-pyrrolidone N-as raw material.In the blanket of nitrogen below normal temperature, be 180rpm, reacted 1 hour the speed setting of stirrer.Then, one side is with the reaction liquid air cooling, and one side adds 20.3g m-phthaloyl chloride, 19.1g 4 again, and 4 '-di-2-ethylhexylphosphine oxide (2-methyl cyclohexane alkanamine), 160g N-N-methyl-2-2-pyrrolidone N-carry out about 3 hours stirring reaction, synthesizing polyamides varnish.Gained reaction liquid (varnish) is injected excessive methyl alcohol, separate out toner with the mixer stirring.With this powder of methanol cleaning, dry at normal temperatures, at about 150 ℃ of following drying under reduced pressure, be dissolved in again in the N-N-methyl-2-2-pyrrolidone N-then, obtain polyamide varnish.
The weight average molecular weight of varnish (Mw) is 32000, and resinous principle content is 20.2 weight %.In addition, prepare the film of about 25 μ m, measure its physics value, the result, oxygen permeability is 490cc/m
2My god, glass transition temperature is 161 ℃, the bonding strength under 150 ℃ of temperature is 13.2N/15mm.
The vacuum heat-insulating plate embodiment's 6 of＜use polyamide melted material 6 preparation 〉
Synthetic polyamide melted material 6 is used for the sealing layer of sheathing material, operate equally, prepare vacuum heat-insulating plate example 6 with vacuum heat-insulating plate example 1.In addition, the size of core is 500mm * 300mm * 10mm.
The vacuum heat-insulating plate example 6 that obtains like this (thickness: measure equally, and under 10 ℃ condition, the initial stage pyroconductivity is 4.2mW/mK, and the pyroconductivity after carrying out 1 month deterioration test under 150 ℃ is 5.1mW/mK by pyroconductivity about 8mm) and thermal shield example 1.
As mentioned above, even vacuum heat-insulating plate of the present invention can not worsen under hot environment in time yet, can the maintaining heat conductivity.
The varnish of the polyimide melted material 1 shown in the embodiment 1 is infiltrated up in the glass fibre, dry under about 90 ℃, the prepreg of preparation semi-cured state.On the alloy foil of the about 15 μ m of thickness, above-mentioned prepreg is set forms the frame shape, place the alloy foil of homotype thereon, use hotpress under about 200 ℃ temperature, to apply 0.83kg/cm
2Pressure, preparation is with the sheathing material of the airtight sealing of three parts.
With fiber diameter the ageing that the glass wool of 3 μ m carried out under 180 ℃ 1 hour, as core.In sheathing material, pack into the getter (molecular sieve 13X/ active carbon) of core and adsorbed gas.In final sealed department office above-mentioned prepreg is set, does the rotary pump exhaust 10 minutes of vacuum package machine, used the diffusion pump exhaust again 10 minutes, make the internal pressure of vacuum heat-insulating plate reach 1.3Pa, then, with heat sealing machine with end seal.
The vacuum heat-insulating plate example 7 that obtains like this with thermal shield 1 same mensuration (thickness: pyroconductivity about 8mm), under 10 ℃ condition, the initial stage pyroconductivity is 4.2mW/mK, the pyroconductivity after carrying out 1 month deterioration test under 200 ℃ is 5.4mW/mK.As mentioned above, even vacuum heat-insulating plate of the present invention can not worsen under hot environment in time yet, can the maintaining heat conductivity.
With the glass wool material of fiber diameter 6 μ m as core, preparation vacuum heat-insulating plate example 8 similarly to Example 1.
The vacuum heat-insulating plate example 8 that obtains like this (thickness: pyroconductivity about 8mm), measure equally with thermal shield example 1, under 10 ℃ condition, the initial stage pyroconductivity is 6.2mW/mK, the pyroconductivity after carrying out 1 month deterioration test under 160 ℃ is 9.8mW/mK.
As mentioned above, even vacuum heat-insulating plate of the present invention can not worsen under hot environment in time yet, can the maintaining heat conductivity.But, if the glass wool fiber diameter is 6 μ m, then the initial value of pyroconductivity increases.
Synthesizing of＜polyimide melted material 9 〉
In the separable flask of stirrer has been installed, the cooling tube of the condenser valve with the cock of band silicone rubber is installed, constitute reaction tank, in this reaction tank, as raw material, add 9.9g dicyclo (2,2,2) suffering-7-alkene-2,3,5,6-tetracarboxylic dianhydride, 2g 3,4 '-diamino-diphenyl ether, 6.5g 1,7-diaminourea heptane, 200g N-N-methyl-2-2-pyrrolidone N-and 30g toluene.Stirred 10 minutes at normal temperatures with in the blanket of nitrogen, the content with reaction tank is warming up to 180 ℃ then, and the speed setting of stirrer is 180rpm, reacts 1 hour.Then, with the reaction liquid air cooling, add 14.7g 3 again, 3 ', 4,4 '-diphenyl tetracarboxylic dianhydride, 16.1g3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 10.4g 1,7-diaminourea heptane, 160g N-N-methyl-2-2-pyrrolidone N-and 30g toluene are warming up to 180 ℃ of stirring reactions that carry out 2.0 hours once more.Therebetween, the rotating speed of stirrer is 180rpm, and the water that generates is discharged from the silicone rubber cock, has synthesized polyimide varnish.
The weight average molecular weight of varnish is 180000, and resinous principle content is 20 weight %.In addition, prepare the film of about 25 μ m, measure its physics value, the result, oxygen permeability is 390cc/m
2My god, glass transition temperature is 152 ℃, the bonding strength under 150 ℃ of temperature is 8.5N/15mm.
The vacuum heat-insulating plate embodiment's 9 of＜use polyimide melted material 9 preparation 〉
The sealing layer of sheathing material uses synthetic polyimide melted material 8, in addition operates preparation vacuum heat-insulating plate example 9 equally with vacuum heat-insulating plate example 1.
The vacuum heat-insulating plate example 9 that obtains like this (thickness: pyroconductivity about 8mm), measure equally with thermal shield example 1, under 10 ℃ condition, the initial stage pyroconductivity is 5.2mW/mK, the pyroconductivity after carrying out 1 month deterioration test under 200 ℃ is 18.5mW/mK.
Hence one can see that, compare with prior art products, suppressed thickness, in addition, though under common temperature, play insulation effect, if but the glass transition temperature of the resin that the welding layer uses is below 160 ℃, bonding strength under 150 ℃ of temperature is below the 10N/15mm, then under high temperature condition, because heating reduces bonding force, vacuum heat-insulating plate destroys, and can't suppress long-term pyroconductivity deterioration.Therefore, the purposes of such thermal shield must be defined in the goods of the highest 130 ℃ of temperature for example or the goods that short-term is used.
The pyroconductivity of (before the deterioration) was 18～22mW/mK when in addition, the frequent at present polyurethane resin that uses used beginning
The sealing layer of sheathing material uses above-mentioned epoxy resin melted material, in addition operates preparation vacuum heat-insulating plate example 10 equally with vacuum heat-insulating plate example 1.
The vacuum heat-insulating plate example 10 that obtains like this (thickness: pyroconductivity about 8mm), measure equally with thermal shield example 1, under 10 ℃ condition, the initial stage pyroconductivity is 6.5mW/mK, and the pyroconductivity after carrying out 1 month deterioration test under 160 ℃ is 18.4mW/mK.
Hence one can see that, compares with prior art products, played the effect that suppresses thickness, if but the welding layer uses epoxy resin, and then the cementability with stainless steel foil reduces, and under high temperature condition, because heating can destroy vacuum heat-insulating plate, can't suppress the pyroconductivity deterioration.
The sealing layer of sheathing material uses above-mentioned polypropylene homopolymer, in addition operates preparation vacuum heat-insulating plate example 11 equally with vacuum heat-insulating plate example 1.
Resulting vacuum heat-insulating plate example 11 (thickness: pyroconductivity about 8mm), measure equally with thermal shield example 1, under 10 ℃ condition, the initial stage pyroconductivity is 4.9mW/mK.Yet when carrying out 1 month deterioration test under 160 ℃, weld is damaged, and can't measure pyroconductivity.Therefore, compare with prior art products, though have the effect that suppresses thickness, under than the high temperature of the glass transition temperature of welding layer resin, vacuum heat-insulating plate can't use.
Claims (12)
1. vacuum heat-insulating plate, this vacuum heat-insulating plate has: the core of inorfil, getter and the metal foil sheathing material that covers above-mentioned core and getter, also has welding layer with the edge section sealing of above-mentioned sheathing material, inner pressure relief with above-mentioned sheathing material, it is characterized in that above-mentioned welding layer forms or be arranged to have the frame shape shape of one or more opening portions.
2. the described vacuum heat-insulating plate of claim 1 is characterized in that, above-mentioned welding layer contains organic polymer, and the oxygen permeability of described welding layer under thickness 25 μ m is 500cc/m
2Below it.
3. the described vacuum heat-insulating plate of claim 1 is characterized in that, above-mentioned welding layer comprises at least a in polyimide resin, polyamide-imide resin, Polyimidesiloxane resin, the polyamide resin.
4. the described vacuum heat-insulating plate of claim 3 is characterized in that, the glass transition temperature of above-mentioned resin is 160～230 ℃.
5. the described vacuum heat-insulating plate of claim 1 is characterized in that, above-mentioned welding layer under 150 ℃ with bonding strength sheathing material be more than the 10N/15mm.
6. the described vacuum heat-insulating plate of claim 1 is characterized in that, above-mentioned metal foil is stainless steel foil or alloy foil.
7. the described vacuum heat-insulating plate of claim 1 is characterized in that, above-mentioned core is that fiber diameter is the glass wool of 3～5 μ m.
8. the described vacuum heat-insulating plate of claim 1 is characterized in that, above-mentioned welding layer is at least a in the filming of solution coat, film or the nonwovens dipping body.
9. body of thermal insulating box, this body of thermal insulating box has by the insulation part of heating equipment heating and is used to keep the heat insulating member of the state of temperature of above-mentioned insulation part, it is characterized in that, above-mentioned heat insulating member is a vacuum heat-insulating plate, this vacuum heat-insulating plate has: the metal foil sheathing material of the core of inorfil, getter, the above-mentioned core of covering and getter and have frame shape shape and with the welding layer of the edge section of above-mentioned sheathing material sealing, with the inner pressure relief of above-mentioned sheathing material.
10. the described body of thermal insulating box of claim 9 is characterized in that, above-mentioned welding layer comprises at least a in polyimide resin, polyamide-imide resin, Polyimidesiloxane resin, the polyamide resin.
11. the described body of thermal insulating box of claim 9 is characterized in that, above-mentioned welding layer is made of at least a in the filming of solution coat, film or the nonwovens dipping body.
12. the described body of thermal insulating box of claim 9 is characterized in that, the maximum temperature of above-mentioned insulation part is 150～220 ℃.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006219138 | 2006-08-11 | ||
| JP2006219138A JP2008045580A (en) | 2006-08-11 | 2006-08-11 | Vacuum heat insulating panel and equipment equipped therewith |
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| Publication Number | Publication Date |
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| CN101122360A CN101122360A (en) | 2008-02-13 |
| CN100516626C true CN100516626C (en) | 2009-07-22 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2007101403461A Expired - Fee Related CN100516626C (en) | 2006-08-11 | 2007-08-09 | Vacuum heat-insulating board and instrument with the same |
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| Country | Link |
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| JP (1) | JP2008045580A (en) |
| KR (1) | KR20080014644A (en) |
| CN (1) | CN100516626C (en) |
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| JP2009293708A (en) * | 2008-06-05 | 2009-12-17 | Hitachi Appliances Inc | Vacuum heat insulating material, apparatus having the same and method of manufacturing vacuum heat insulating material |
| JP5178332B2 (en) * | 2008-06-12 | 2013-04-10 | 旭化成せんい株式会社 | Hot water storage |
| JP2010032175A (en) * | 2008-07-31 | 2010-02-12 | Hitachi Appliances Inc | Heat pump water heater |
| JP5308783B2 (en) * | 2008-07-31 | 2013-10-09 | 日立アプライアンス株式会社 | Heat pump water heater |
| EP2399661B1 (en) * | 2009-03-24 | 2017-01-18 | Panasonic Corporation | Fabrication method for gas-adsorbing device, gas-adsorbing device, and method of using the same |
| CN102102796B (en) * | 2010-03-12 | 2012-10-17 | 福建赛特新材股份有限公司 | Vacuum insulation panel and manufacturing method thereof |
| CN101876391A (en) * | 2010-05-24 | 2010-11-03 | 上海晨华电炉有限公司 | High-temperature vacuum thermal-insulating plate capable of insulating temperature above 350 DEG C |
| CN101900473A (en) * | 2010-07-27 | 2010-12-01 | 王欣南 | Built-in integral L-shaped vacuum heat insulation slab for refrigerator and processing method thereof |
| JP5261616B2 (en) * | 2011-02-14 | 2013-08-14 | パナソニック株式会社 | Gas adsorption device and vacuum heat insulating material provided with the same |
| JP5335149B2 (en) * | 2011-05-25 | 2013-11-06 | 積水フイルム株式会社 | Gas barrier composite film and vacuum heat insulating material using the same |
| KR101323490B1 (en) | 2011-08-23 | 2013-10-31 | (주)엘지하우시스 | Vacuum insulation panel with moisture-gas adsorbing getter material and manufacturing method thereof |
| JP5741397B2 (en) * | 2011-11-17 | 2015-07-01 | 三菱電機株式会社 | Manufacturing method of cooking device |
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| KR101783074B1 (en) * | 2013-03-12 | 2017-09-29 | (주)엘지하우시스 | Envelope including glass fiber for vacuum insulation panel and vacuum insulation panel having the same |
| CN103422632B (en) * | 2013-07-17 | 2016-03-30 | 戴长虹 | There is composite evacuated plate of the stone material of getter and preparation method thereof |
| CN104964124A (en) * | 2014-08-01 | 2015-10-07 | 常州山由帝奥绝缘材料制造有限公司 | Vacuum insulation board having gaps and/or through holes and method for producing same |
| EP3197679B1 (en) * | 2014-09-25 | 2019-11-06 | Basf Se | Method for manufacturing a composite element for vacuum insulation elements |
| KR102466469B1 (en) | 2015-08-03 | 2022-11-11 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| KR102525551B1 (en) | 2015-08-03 | 2023-04-25 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| KR102502160B1 (en) * | 2015-08-03 | 2023-02-21 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| KR102529852B1 (en) * | 2015-08-03 | 2023-05-08 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| KR102456642B1 (en) | 2015-08-03 | 2022-10-19 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| KR102529853B1 (en) | 2015-08-03 | 2023-05-08 | 엘지전자 주식회사 | Vacuum adiabatic body, fabricating method for the Vacuum adiabatic body, porous substance package, and refrigerator |
| KR102442973B1 (en) | 2015-08-03 | 2022-09-14 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| KR102498210B1 (en) | 2015-08-03 | 2023-02-09 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| KR102466446B1 (en) * | 2017-12-13 | 2022-11-11 | 엘지전자 주식회사 | Vacuum adiabatic body and refrigerator |
| FR3083682B1 (en) * | 2018-07-12 | 2020-12-11 | Ethera | ANTI-ODOR COVER |
| CN111089223A (en) * | 2019-12-19 | 2020-05-01 | 福建赛特冷链科技有限公司 | Vacuum insulation panel of composite pipeline |
| JP7273772B2 (en) * | 2020-10-21 | 2023-05-15 | プライムプラネットエナジー＆ソリューションズ株式会社 | LAMINATED ELECTRICITY STORAGE DEVICE MANUFACTURING METHOD AND LAMINATED ELECTRICITY STORAGE DEVICE INSPECTION METHOD |
| CN113251243A (en) * | 2021-04-30 | 2021-08-13 | 广东美的厨房电器制造有限公司 | Film material for vacuum insulation panel, vacuum insulation panel and preparation method of vacuum insulation panel |
| CN113915458B (en) * | 2021-11-02 | 2023-04-18 | 英索来欣(苏州)新材料科技有限公司 | Vacuum insulation panel core material |
| CN114132022B (en) * | 2021-11-02 | 2022-08-16 | 河海大学 | Wedge-shaped lining plate for hard brittle high-modulus magnesium alloy and edge crack control rolling method and application thereof |
| CN116066663B (en) * | 2023-02-15 | 2023-11-28 | 南通远顺耐纤有限公司 | Glass fiber core material heat insulation plate and preparation method thereof |
-
2006
- 2006-08-11 JP JP2006219138A patent/JP2008045580A/en active Pending
-
2007
- 2007-08-09 CN CNB2007101403461A patent/CN100516626C/en not_active Expired - Fee Related
- 2007-08-09 KR KR1020070079850A patent/KR20080014644A/en not_active Application Discontinuation
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| KR20080014644A (en) | 2008-02-14 |
| CN101122360A (en) | 2008-02-13 |
| JP2008045580A (en) | 2008-02-28 |
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