CN101251222B - High-strength, flame-proof vacuum insulation plate and manufacture method thereof - Google Patents
High-strength, flame-proof vacuum insulation plate and manufacture method thereof Download PDFInfo
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- CN101251222B CN101251222B CN2008100612055A CN200810061205A CN101251222B CN 101251222 B CN101251222 B CN 101251222B CN 2008100612055 A CN2008100612055 A CN 2008100612055A CN 200810061205 A CN200810061205 A CN 200810061205A CN 101251222 B CN101251222 B CN 101251222B
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- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000000034 method Methods 0.000 title 1
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- 238000007789 sealing Methods 0.000 claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000006260 foam Substances 0.000 claims description 18
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- 239000005030 aluminium foil Substances 0.000 claims description 6
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 4
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- 238000009826 distribution Methods 0.000 claims description 4
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- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
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- LYCAIKOWRPUZTN-NMQOAUCRSA-N 1,2-dideuteriooxyethane Chemical compound [2H]OCCO[2H] LYCAIKOWRPUZTN-NMQOAUCRSA-N 0.000 claims description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 claims description 2
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 claims description 2
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- 229920005830 Polyurethane Foam Polymers 0.000 claims description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
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- 229940058401 polytetrafluoroethylene Drugs 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
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- 239000002994 raw material Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 239000011162 core material Substances 0.000 abstract description 38
- 239000004964 aerogel Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
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- 239000010410 layer Substances 0.000 description 51
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 13
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- 230000001070 adhesive effect Effects 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
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- 239000004642 Polyimide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
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- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 239000003463 adsorbent Substances 0.000 description 1
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- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
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- Laminated Bodies (AREA)
Abstract
The invention discloses a high-strength and flame-resistant vacuum insulating board which comprises core material and a sealing film wrapped outside the core material. The core material comprises an intermediate layer, thermal insulation material layers are respectively superposed above and below the intermediate layer, the sides of the insulation material layers above and below the intermediate layer facing toward the intermediate layer are corrugated surfaces, corrugated depressions of the corrugated surfaces are filled with silicon dioxide aerogel and getter, the sides of the insulation material layers back against the intermediate layer are planes, and the planes are adhered with reflection layers. The vacuum insulating board of the invention has a stable structure, better impact-resistant property, strong flame resistance, good moderated and high temperature resistant performance and long service life, and can be repetitively pumped to use.
Description
Technical field
The present invention relates to a kind of heat-insulation material, relate in particular to a kind of high-intensity vacuum heat-insulating plate and preparation method thereof.
Background technology
The existing vacuum heat-insulating plate of existing vacuum heat-insulating plate (VIP plate) normally is provided with adiabatic core in the multilayer package bag, with the vacuum pumping of multilayer package bag, and in the multilayer package bag, adsorbent is set, improve vacuum in the multilayer package bag, under the situation identical, can significantly reduce the thickness of heat insulation layer with antivacuum heat insulating effect.
A kind of vacuum heat-insulating plate is disclosed as Chinese utility model patent 200420053407.2, comprise shell and the adiabatic core that is arranged in the vacuum casting, described core comprises aerosil and glass fibre, described glass fibre is interwoven between the aerosil, and the surface of described core is provided with infrared reflecting layer.Described shell is stacked bag or hard metal or glass plate.
200610122871.6 be vacuum heat-insulating plate of core and preparation method thereof with the phenolic aldehyde, relate to a kind of VIP plate, provide a kind of core price lower, good flame resistance be the VIP plate and the preparation method of core with the foaming phenolic aldehyde.Its minor face that consists of at the phenolic core material plate is provided with slotted eye, puts getter in the slotted eye, in phenolic core material plate peripheral hardware barrier bag.During preparation with phenol, heat up in formalin and the NaOH adding reactor, be heated to boiling, add the formic acid neutralization after the cooling, discharging behind water and unreacted aldehyde and the phenol is sloughed in decompression, foaming brushes away the core floating dust, establishes the slotted eye of placing getter and puts into getter at phenolic core material plate minor face, place the vacuum chamber exhaust to heat in phenolic aldehyde, record the time, the back cooling is handled in insulation, when the vacuum room temperature drops to below 80 ℃, open vacuum chamber and take out phenolic core material, pack into packaging bag and put the vacuum chamber exhaust into mixes up cylinder pressure, heating-up temperature and sealing the time is sealed, put into atmosphere, take out the VIP plate.
But in the prior art, the general intensity of vacuum heat-insulating plate is not high, and impact resistance is poor, and is high temperature resistant and fire resistance is undesirable.
Summary of the invention
The invention provides a kind of high strength, resistant to elevated temperatures vacuum heat-insulating plate.
A kind of high strength, flame-proof vacuum insulation plate, comprise core and the sealing film that is wrapped in the core outside, described core comprises the intermediate layer, the upper and lower in intermediate layer is stacked with insulation material layer respectively, described intermediate layer is an aluminium foil, and the side of the insulation material layer of intermediate layer upper and lower towards the intermediate layer is corrugated surface, is filled with aerosil and getter in the ripple depression of corrugated surface, an insulation material layer side in intermediate layer dorsad is the plane, and this plane is stained with the reflecting layer.
The preferred hydrophobic type aerosil of described aerosil, getter are barium one lithium getter.The weight ratio of aerosil and getter is 100: 1～25.
Described reflector material can adopt aluminium foil, and the adhesive that is used for bonding insulation material layer and reflecting layer is selected from the JSF stick, polyurethane adhesive, organosiloxane coupling agent or polyimides adhesive etc.
Described sealing film is that ester film, polyethylene film, poly tetrafluoroethylene, pvf film or polypropylene screen etc. are closed in polyimide film, poly-organosilicon resin molding, poly-insatiable hunger, and sealing film thickness is 10～100 μ m.Only with the side environmental sealing of core, the upper and lower faces of core is owing to being stained with reflecting layer and also airtight, so do not need to be wrapped in the sealing film for sealing film.Because the needs that vacuumize, can on the sealing film of any side, open the aperture of a diameter at 2～5mm, be filled with viscoelastic rubber or polyurethane etc. in the aperture, when vacuumizing, pass viscoelastic rubber or polyurethane by vent wire vacuum heat-insulating plate internal cavities and outer vacuum chamber or vavuum pump are communicated with.
The insulation material layer of described intermediate layer upper and lower its ripple direction when stacked is not parallel to each other, and is preferred vertical mutually, to reach higher intensity.
The material of described insulation material layer is phenolic foam, poly(urea formaldehyde) foamed plastics, polystyrene foam plastics, polyurethane foam plastics, foamed polyolefine plastic or Vestolit, preferred phenolic foam, phenolic foam specifically can be selected phenolic aldehyde polystyrene foam plastics, phenolic aldehyde expanded perlite syntactic foam, phenol formaldehyde foam glass syntactic foam or fiber reinforcement phenolic foam for use.The thickness of insulation material layer (comprising corrugated portion) is 3～12mm, and wherein the degree of depth of ripple depression is 2～8mm.
The aluminium foil in described intermediate layer can be two-sided aluminium film of fibrous paper or the two-sided aluminium film of plastics, and thickness is 1～10 μ m, and the intermediate layer has some apertures, and the aperture is 1～3mm, so that keep the circulation of air when vacuumizing, the distribution density of aperture is 0.1～0.5/cm
2
The outer surface that vacuum heat-insulating plate of the present invention contains undulatory core is the plane, can improve the mechanics shock resistance of its structure greatly, and make heat pass through the conduction of corrugated projection wall, and both reduced heat transfer area, played the effect of supporting complete skeleton again.The two-layer modes of emplacement that contains undulatory core is the vertically opposite placement of striped, thereby makes that two-layer sheet material of contact and middle aluminium foil layer are that point or line contact, thereby has reduced heat transfer area.Environmental sealing film around core can reduce the heat bridge that the edge causes so greatly.Be coated with the reflecting layer at the two-layer outer surface that contains the insulation material layer of ripple, thereby effectively reduced the infrared radiant heat conduction, improved heat-insulating property.In the corrugated cavity, insert an amount of aeroge and can reduce thermal conductivity factor.Since at sealing film one viscoelastic closed hole is arranged, after date when using a section, and heat-proof quality can descend, and can penetrate again with pin hole to bleed, and to keep good performance, increases the service life.
The material of described insulation material layer is a phenolic foam, and phenolic foam is made by the raw material mixing post-foaming of following weight ratio:
Resol 100
Silicone oil 1～3
Urea 5～10
Inorganic filler 0～30
Water 30～60
Curing agent 20～30
Described inorganic filler is foaming clay or kaolin;
Described blowing agent weight ratio consists of benzinum and pentane 2～4: 2;
Described curing agent weight ratio consists of benzene sulfonic acid and phosphatase 11: 2～3.
The preparation method of vacuum heat-insulating plate of the present invention, the preferred phenol formaldehyde foam of the material of insulation material layer wherein, the preparation method is as follows:
(1) by weight with after resol, ethylene glycol, DC-193 silicone oil, urea, inorganic filler, water and the blowing agent mixing, add curing agent, stir and pour mould into, put into temperature and be 80 ℃ baking oven foaming, take out to the fixing back of foam, obtaining phenol formaldehyde foam and be the heat-insulating material layer material and cutting into a side is the shape on plane for the corrugated surface opposite side;
(2) intermediate layer material is cut into required size, open a certain amount of aperture, small aperture is 1～3mm, and the distribution density of aperture is 0.1～0.5/cm
2
(3) two phenol formaldehyde foams and the intermediate layer with well cutting stacks together, and the ripple direction of upper and lower two phenol formaldehyde foams is vertical, and puts into aerosil and getter in its ripple depression, obtains core;
(4) with sealing film with environmental sealing around the core, open an aperture in sealing film one side, hole diameter fills up viscoelastic fluid sealant sealing again at 2～5mm in aperture;
(5) reflector material is cleaned up, at one side coating adhesive;
(6) reflector material behind the coating adhesive is pressed to the upper and lower surface of the core of edge good seal,, the upper and lower surface of core is sealed fully at 180 ℃ of hot pressings;
(7) will seal good core and in vacuum heat treatment furnace, vacuumize, and heating, the absolute vacuum degree is controlled at 5～10Pa, and programming rate is controlled at 5～15 ℃/min, and maximum temperature is 160～320 ℃.After temperature reaches maximum temperature, be incubated to the vacuum of the vacuum chamber of vacuum heat treatment furnace be 5Pa, temperature retention time 0.5～2h, cooling obtains vacuum heat-insulating plate.
When this phenol formaldehyde foam of preparation, the adding of urea modifier can improve the toughness of phenol formaldehyde foam, helps improving the mechanical property of vacuum heat-insulating plate.The density of phenol formaldehyde foam should be controlled at 60～105kg/m
3, density is too little can not bear atmospheric pressure and pressed and collapse, and density is too big, then will certainly increase thermal conductivity factor, increases the weight of vacuum heat-insulating plate, also can improve production cost simultaneously.
The aperture of phenol formaldehyde foam is the smaller the better, can reduce thermal conductivity factor like this; Phenolic core material will have certain toughness, can not be too crisp, can not fall slag.
Vacuum heat-insulating plate of the present invention and existing vacuum heat-insulating plate structure compared are stable, and better impact resistance is arranged.Anti-flammability is strong, and anti-middle high-temperature behavior is good, can be anti-for a long time-180 ℃～250 ℃, and long service life can be used by repeatedly pumping.
Description of drawings
Fig. 1 is a vacuum heat-insulating plate exploded sketch of the present invention;
Fig. 2 is a vacuum heat-insulating plate perspective view of the present invention.
The specific embodiment
Referring to accompanying drawing, high strength of the present invention, flame-proof vacuum insulation plate, comprise core and the sealing film that is wrapped in the core outside, core comprises intermediate layer 2, on the intermediate layer 2, the below is stacked with insulation material layer 1a and insulation material layer 1b respectively, described intermediate layer 2 is the two-sided aluminium film of fibrous paper, a side of 2 is a corrugated surface towards the intermediate layer for insulation material layer 1a and insulation material layer 1b, be filled with aerosil and getter in the ripple depression of corrugated surface, insulation material layer 1a and insulation material layer 1b a side in intermediate layer 2 dorsad are the plane, this plane is stained with the reflecting layer, and for example the planar side of insulation material layer 1 is stained with reflecting layer 3.
Sealing film 41, sealing film 42, sealing film 43 and sealing film 44 are with the side environmental sealing of core, open an aperture 6 on the sealing film 41, be filled with viscoelastic polyurethane in the aperture 6, the ripple side of insulation material layer 1a and insulation material layer 1b is vertical mutually, to reach higher intensity, have some apertures on the intermediate layer 2.
Vacuum heat-insulating plate preparation 1
Resol powder 100g and foaming clay 20g are mixed, add again and add entry 50g and urea 6g after ethylene glycol 2.5g, DC-193 silicone oil 2g and blowing agent 9g mix, add curing agent 26g at last, stir and pour mould into,
Put into temperature and be 80 ℃ baking oven foaming, solidify the back to foam and take out, obtain phenol formaldehyde foam.
The blowing agent weight ratio consists of benzinum: pentane=2: 1;
The curing agent weight ratio consists of benzene sulfonic acid: phosphoric acid=1: 2;
Adopt not saturating steel blade of corrugated and straight shape blade to cut phenol formaldehyde foam, obtain required shape, a side is that another example of corrugated surface is the plane.
Ripple thickness: core gross thickness=2: 3, core gross thickness are 3mm, brush away the floating dust on phenol formaldehyde foam surface after foam is cut into;
Get the two-sided aluminium film of fibrous paper as intermediate layer 2, thickness is 5 μ m, opens a certain amount of aperture therein, and the aperture is 2mm, and the distribution density in hole is 0.5/cm2, cuts into required size.
The phenol formaldehyde foam and the intermediate layer of well cutting are superimposed, and upper and lower two phenol formaldehyde foam ripple directions are vertical, and put into aerosil and getter in its ripple cavity, and getter adopts barium one lithium getter, obtains core.
The Kapton that with thickness is 50 μ m is opened an aperture with environmental sealing around the core on the Kapton, hole diameter is 3mm, fills up viscoelastic high temperature resistant organosilicon sealant sealing again in aperture.
Getting two heat reflection metal aluminum foils cleans up, cover the polyimide adhesive of one deck gas-barrier property in the one side, the upper and lower faces (being plane one side of phenol formaldehyde foam) that is adhered to core respectively obtains packaged plate body at 180 ℃ of hot pressings, the thickness of heat reflection metal aluminum foil 3 is 15 μ m, and the polyimide adhesive layer thickness is 200 μ m.
Penetrate aperture with syringe needle, place vacuum heat treatment furnace to vacuumize packaged plate body, and heat, vacuum degree control is at 5～10Pa, and programming rate is controlled at 10 ℃/min, and maximum temperature is 320 ℃.After temperature reaches maximum temperature, be incubated to vacuum degree in vacuum chamber be 1Pa, after handling, extract syringe needle, treat its cooling, take out and to obtain the vacuum insulation board finished product.
Vacuum heat-insulating plate preparation 2
According to the flow preparation vacuum heat-insulating plate of vacuum heat-insulating plate preparation process 1, difference is that PREPARATION OF PHENOLIC FOAM is:
Resol powder 100g and kaolin 20g are mixed, add again and add entry 40g and urea 9g after ethylene glycol 2g, DC-193 silicone oil 1.5g and blowing agent 8g mix, add curing agent 20g at last, stir and pour mould into,
Put into temperature and be 80 ℃ baking oven foaming, solidify the back to foam and take out, obtain phenol formaldehyde foam.
The blowing agent weight ratio consists of benzinum: pentane=3: 1;
The curing agent weight ratio consists of benzene sulfonic acid: phosphoric acid=1: 1.5.
Claims (6)
1. a high strength, flame-proof vacuum insulation plate, comprise core and the sealing film that is wrapped in the core outside, described core comprises the intermediate layer, the upper and lower in intermediate layer is stacked with insulation material layer respectively, described intermediate layer is an aluminium foil, the side of the insulation material layer of intermediate layer upper and lower towards the intermediate layer is corrugated surface, be filled with aerosil and getter in the ripple depression of corrugated surface, the weight ratio of aerosil and getter is 100: 1～25, an insulation material layer side in intermediate layer dorsad is the plane, and this plane is stained with the reflecting layer;
The material of described insulation material layer is a phenolic foam, and phenolic foam is made by the raw material mixing post-foaming of following weight ratio:
Resol 100
Ethylene glycol 2～3
Silicone oil 1～3
Urea 5～10
Inorganic filler 0～30
Water 30～60
Blowing agent 6～10
Curing agent 20～30
Described inorganic filler is foaming clay or kaolin;
Described blowing agent weight ratio consists of benzinum and pentane 2～4: 2;
Described curing agent weight ratio consists of benzene sulfonic acid and phosphatase 11: 2～3.
2. high strength as claimed in claim 1, flame-proof vacuum insulation plate is characterized in that: described reflector material is an aluminium foil.
3. high strength as claimed in claim 1, flame-proof vacuum insulation plate, it is characterized in that: described sealing film is that ester film, polyethylene film, poly tetrafluoroethylene, pvf film or polypropylene screen are closed in polyimide film, poly-organosilicon resin molding, poly-insatiable hunger, and sealing film thickness is 10～100 μ m.
4. high strength as claimed in claim 1, flame-proof vacuum insulation plate is characterized in that: the ripple direction of the insulation material layer of top, described intermediate layer is vertical mutually with the ripple direction of the insulation material layer of below, intermediate layer.
5. high strength as claimed in claim 1, flame-proof vacuum insulation plate is characterized in that: the material of described insulation material layer is phenolic foam, poly(urea formaldehyde) foamed plastics, polystyrene foam plastics, polyurethane foam plastics, foamed polyolefine plastic or Vestolit.
6. high strength as claimed in claim 1, flame-proof vacuum insulation plate is characterized in that: described intermediate layer has some apertures, and small aperture is 1～3mm, and the distribution density of aperture is 0.1～0.5/cm
2
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| CN2008100612055A CN101251222B (en) | 2008-03-20 | 2008-03-20 | High-strength, flame-proof vacuum insulation plate and manufacture method thereof |
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| CN2008100612055A CN101251222B (en) | 2008-03-20 | 2008-03-20 | High-strength, flame-proof vacuum insulation plate and manufacture method thereof |
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| CN101251222B true CN101251222B (en) | 2010-09-08 |
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| WO2010030890A2 (en) * | 2008-09-15 | 2010-03-18 | Thin Thermal Barriers Limited | Thermal resistor material |
| CN101799099B (en) * | 2010-04-16 | 2011-08-31 | 中国人民解放军国防科学技术大学 | Nanometer multiple-layer composite thermal insulation material and preparation method thereof |
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2008
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