CN100532910C - Vacuum heat insulation material and cold reserving apparatus with the same - Google Patents

Abstract

An outer coating material (13) of a vacuum heat insulation material is a layered body made by layering, with adhesive agent layers (25, 26) in between, a sealant layer (21), a metal layer (22), a first plastic film layer (23), and a second plastic film layer (24), in that order from the inner side. When the vacuum heat insulation material is pierced by a foreign object, one layer in the inside of the layered body shuts off propagation of breakage caused by the piercing to prevent production of a through pin hole. By use of the outer coating material with high gas barrier ability and excellent pin hole resistance against piercing by a fine foreign object, a high-quality vacuum heat insulation material capable of maintaining excellent heat insulation performance for a long period is obtained.

Description

Vacuum thermal insulating material and, be equipped with the cold insulation equipment of Vacuum thermal insulating material

Technical field

The present invention relates to by core and outer packaging material constitute, core also made inner pressure relief enclosed vacuum thermoinsulation material by outer packaging material coating.

Background technique

In recent years, energy problem and environmental problem become a urgent subject, and people have carried out all discussions to the method that is used for effective use of energy sources.

This problem wherein being paid close attention to is, as energy-conservationization of the tame electrical articles such as refrigerator of civil equipment.In order to realize energy-conservationization of refrigerator, be necessary effectively to utilize cold and hot, be valid approach with the insulated cabinet height thermal insulationization that constitutes the refrigerator framework.For this reason, it is effectively that the thermoinsulation material that will have a high thermal insulation is used for body of thermal insulating box, in recent years, as the high-performance thermoinsulation material, uses with the Vacuum thermal insulating material of glass fibre as core.

Vacuum thermal insulating material is that the core that will be made of porosity inserts in the outer packaging material, inner pressure relief and sealing are constituted.The durability that does not occur pin hole when therefore, above-mentioned outer packaging material is necessary to have the high gas barrier property that can keep internal pressure in long-time and operation.

For this reason, wrapper are made of the olefines sealing film of the thermal fusion welding excellence of the vapor-deposited film of the aluminium foil in the such film of outermost poly-phthalic acid second diester, mesosphere or gas barrier property excellence and innermost layer.

For example, in No. 2568485 communique of Japan Patent, as the Vacuum thermal insulating material of the pin hole excellent in te pins of durability that the damage by outer packaging material is caused, put down in writing to use from skin to internal layer and four closed the heat insulator bag that film forms seal container layer by layer by what nylon film, PETP film, gas barrier layer, polyethylene film constituted.

Yet, because above-mentioned formation in the past, the nylon film of the outermost surface of packaging material is laminated outside traumatic resistance and anti-pin hole excellence, cause the pin hole that produces effective to preventing from the friction of outside and foreign matter, but to having a sufficient durability because foreign matter is sneaked into inside, the pin hole that produces from the sealing layer side of innermost layer is not talkative when the vacuum packaging.

Open in the flat 11-79234 communique the spy,, put down in writing and passed through at 10～70g/m as being applicable to vacuum-packed wrapper ²On the single face of thick paper base material respectively across the laminated wrapper that drawing plastic film, sealing layer arranged and form of bonding layer and on above-mentioned drawing plastic film, be formed with metallic oxide evaporation layer.Utilizing this formation to carry out under the vacuum-packed situation, the formation of the corner angle of packed article parts can be carried out smoothly, and barrier property such as moisture resistance reduces and can diminish after vacuum packaging.

Yet above-mentioned formation in the past, though the pin hole that impact and the friction that suppresses from the outside caused occurs effectively, but foreign matter is sneaked under inner such situation when vacuum packaging, and then because the kind of wrapper, to saying to have sufficient durability by the pin hole that inboard reason produced of innermost layer.

Thereby, open in the flat 9-317986 communique the spy and to disclose, be target so that the high Vacuum thermal insulating material of pin hole durability to being caused by thrusting of foreign matter to be provided, attempt foreign matters being thrust by the intensity of thrusting that improves plastic layer.

Yet, Vacuum thermal insulating material in the past, constitute between the film of outer packaging material by powerful laminated, big by peeling strength between the film of lamination, be subjected to by the sharp-pointed foreign matter in front portion produced to thrust stress and make the reason of film breaks be by the concentrated compression that causes of stress.Compressed object extends in vertical direction, has produced compressive stress and rapid shearing force in vertical direction when breaking.And then by the power of compressing on the Vertical direction that is produced, to being applied tensile stress by the film of lamination, the result is this film breaks at the same time by adhesive material.Therefore, outside being shorter in length than of foreign matter, under the situation of the thickness of packaging material, there is the problem that produces penetration hole.

In addition, open in the 2003-340972 communique the spy and to have put down in writing,, be provided with the weak layer of peeling strength in order to prevent to impact breaking and pin hole of the laminated plastic film that causes.And following impact resistance wrapper are disclosed, promptly, a kind of package bag of ice making thing of the content that mixed frozen food, sharp edges horn shape be housed, even under the low temperature circulation environment, vibration in the transportation can not cause package bag to be broken, or the following drop impact that the error that goods is handled causes broken bag or pin hole can not take place yet.

Figure 12 shows the sectional drawing of impact resistance wrapper in the past.The impact resistance wrapper 96 of Figure 12 on the single face of the base material 91 that is made of synthetic resin layer, are removed the closure part 97 at base material 91 edges, have printing ink layer 95.Comprise printing ink layer 95, on base material 91, be provided with impact resistance resin layer 92 comprehensively.And then, on impact resistance resin layer 92, be provided with sealing layer 94 across bonding layer 93.Other preparation method as impact resistance wrapper 96 has, closure part 97 except base material 91 edges, printing ink layer 95 is set on the single face of base material 91, and then impact resistance resin layer 92 only is set on printing ink layer 95, on impact resistance resin layer 92, across being arranged on the base material 91 bonding layer 93 laminated sealing layers 94 on comprehensively.

Above-mentioned impact resistance wrapper 96 are in the past waited under that falling state etc. brings, the situation from the impact of outside by the interior ice that wrapping being subjected to, even base material 91 breaks, also can peel off, prevent to produce penetration hole by the printing ink layer a little less than the peeling strength 95.

Yet, the laminated film that constitutes above-mentioned existing impact resistance wrapper existing problem points under being applicable to as the situation of the outer packaging material of Vacuum thermal insulating material will be described below.That is,, fail to fit tightly and the unnecessary laminated film self that coats is folding, form countless folds with core because laminate film press to be paid on core by barometric pressure.Consequently there is following problems, that is, and in the laminated film of the printing ink layer with weak peeling strength approaches, because the part printing ink layer has produced fold, so peel off easily between the film substrate.

In addition, in the current packaging material, improving the purpose of anti-pin hole, mainly is to prevent the cracking that is caused by impact and prevent the puncture that the such bulk content with shape to a certain degree of ice making thing causes.Therefore, the problem that exists for outer packaging material as Vacuum thermal insulating material, promptly for the pin hole that causes by the such small foreign matter of glass fibre, glass slag or dust, its anti-pin hole to improve effect also insufficient.

And then different with common vacuum-packed body, Vacuum thermal insulating material need be kept high vacuum in long-time like this in 10 years, and like this, laminated film need have high gas barrier property.Therefore, the current packaging material, because gas barrier property is insufficient, heat-insulating property reduces as time goes by, therefore is not suitable for the outer packaging material of using as Vacuum thermal insulating material.

Summary of the invention

The objective of the invention is to solve above-mentioned existing problem,, be provided at the long-time interior Vacuum thermal insulating material heat-insulating property excellence, high-quality by the laminated film of the gas barrier property with excellent needle resistance and excellence is provided.

In order to solve above-mentioned existing problem, the invention provides the outer packaging material that has core and coat core, and the inside of outer packaging material is depressurized sealing and the Vacuum thermal insulating material of formation, it is characterized in that, outer packaging material is the plastic pellicle that comprises more than 2 layers, the laminating body of metal layer and their bonding layer of bonding, this laminating body is to have the laminating body that stress relaxes structure at internal layer, this stress relaxes the rupture propagation that structure can prevent to run through the Vertical direction of this laminating body effect, under the situation that foreign matter thrusts, can thrust the propagation of breaking that causes by some positions blocking-up, prevent penetration hole in laminating body inside.

Description of drawings

[Fig. 1] Fig. 1 is the sectional drawing of the Vacuum thermal insulating material in the example 1 of the present invention.

[Fig. 2] Fig. 2 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 1 of the present invention.

[Fig. 3] Fig. 3 is the sectional drawing of the test film of the mensuration shear strength among the present invention.

[Fig. 4] Fig. 4 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 2 of the present invention.

[Fig. 5] Fig. 5 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 3 of the present invention.

[Fig. 6] Fig. 6 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 4 of the present invention.

[Fig. 7] Fig. 7 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 5 of the present invention.

[Fig. 8] Fig. 8 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 6 of the present invention.

[Fig. 9] Fig. 9 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 7 of the present invention.

[Figure 10] Figure 10 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the invention process form 8.

[Figure 11] Figure 11 is the sectional drawing of the freezing refrigerator in the invention process form 9.

[Figure 12] Figure 12 is the sectional drawing of impact resistance wrapper in the past.

Symbol description

11 Vacuum thermal insulating material

12 cores

13 outer packaging materials

21 sealing layers

22 metal foil layers

23,29 the 1st plastic film layers

24 the 2nd plastic film layers

25,26 bonding layers

27 evaporation layers

28,48 co-extrusion film layers

51 refrigerators

52 body of thermal insulating box

53 outer containers

Case in 54

55 RPUF

56 dividing plates

57 cold storage rooms

58 refrigerating chambers

59 electric-power damper (damper)

60 fan electromotors

61 defrosting heaters

62 vaporizers

63 compressors

64 condensers

65 capillary tubies

66

Embodiment

Vacuum thermal insulating material of the present invention, be to have the laminating body that is formed by the applying of the plastic pellicle more than 2 layers coats the structure of core as outer packaging material Vacuum thermal insulating material, it is the outer packaging material that has core at least and coat core, and the inside of outer packaging material is depressurized the Vacuum thermal insulating material that is sealed to form, wherein outer packaging material is the plastic pellicle that comprises more than 2 layers, metal layer, and their laminating body of bonding layer of boning, this laminating body possesses the compressive stress that can relax the Vertical direction that connects above-mentioned laminating body and act at internal layer, and the stress that can prevent the propagation of breaking relaxes structure.

Stress relaxes structure and is meant, in the internal layer of above-mentioned laminating body, can block the structure of breaking and propagating to other the plastic pellicle that is adjacent in outer layer side of the plastic pellicle that caused by thrusting of glass slag etc.Therefore, relax structure as stress, because thrusting of foreign matter makes laminating body be subjected under the situation of compressive stress of Vertical direction, at least contain a kind of structure in following 2 kinds of structures, promptly, (1) structure peeled off of a certain interface of above-mentioned laminating body and (2) constitute the structure that one of the plastic pellicle of laminating body or bonding layer break.

Now, if hypothesis is present in the foreign matter with corner angle of the glass slag on surface such as core etc. or the situation that the such small items of dust thrusts outer packaging material, then the inboard film that is thrust by foreign matter since when reducing pressure film be compressed and laterally direction expand.When film breaks, compressive force spreads laterally from thrusting central point.Therefore, in film,, act on the propagation tensile force laterally through adhesive layer from thrusting central point with respect to by the outside film of lamination, that is, and shearing force.

At this moment, the shearing force that adhesive layer is broken than the little situation of shearing force that makes outside film rupture under, adhesive layer is sheared power and breaks in advance.The power of thrusting of foreign matter weakens as a result, thereby can thrust the propagation of power by blocking-up, suppresses laminated film and penetration hole occurs.

And then if having interface a little less than the shear strength or the interface a little less than the peeling strength in laminated film, then because the effect of shearing force, peel off at the weak interface of shear strength or peeling strength, and the feasible thus power of thrusting is weakened.The result has blocked the propagation of the power of thrusting, and penetration hole occurs thereby can suppress laminated film.

So like this, by layer a little less than on the part of laminating body shear strength being set or the interface a little less than the shear strength, can provide and to guarantee sufficient peeling strength, have a laminated film of excellent anti-pin hole simultaneously.

In addition, by laminated film being comprised have the plastic pellicle of metal foil layer or metal evaporation layer or ceramic evaporation layer, can obtain the gas barrier property excellence and long-time in the Vacuum thermal insulating material of heat-insulating property excellence.

Vacuum thermal insulating material of the present invention, can guarantee as the sufficient gas barrier property of the outer packaging material of Vacuum thermal insulating material and have the outer packaging material that the laminated film of excellent anti-pin hole constitutes simultaneously by being equipped with, can be provided at the high-quality Vacuum thermal insulating material that has excellent heat-insulating property in long-time.

The present invention and then relate to the Vacuum thermal insulating material that constitutes across the laminated laminated film of bonding layer by the plastic pellicle more than at least 2 layers.Under the situation that foreign matter thrusts, by in the inside of laminating body the blocking-up of a certain position by thrusting the propagation of breaking that causes, thereby can prevent the penetration hole that runs through outer packaging material integral body.

Usually, thrust under the situation of laminated film at foreign matter etc., owing to the masterpiece that thrusts of foreign matter is the compressive force effect, laminated film breaks.Because in the laminated film that breaks, compressive force is propagated such acting on laterally from the center of breaking, thus as shear action in laminated film.

At this moment, if having weak shear strength layer in that laminated film is inner, because the layer of weak shear strength that has of laminated film inside breaks, makes that the power of thrusting is disperseed relaxes, so can block the downward Es-region propagations of the power of thrusting.The result can prevent to produce penetration hole.

Same in addition, the interface a little less than also can there be shear strength in laminated film inside.In this case, peel off owing to have the interface of weak shear strength in laminated film inside, make the power of thrusting be disperseed mitigation, so can block the downward Es-region propagations of the power of thrusting, the result can prevent to produce penetration hole.

In addition, the interface that layer that shear strength is weak or shear strength are weak is present under the situation of the outermost surface of laminated film and certain one deck at least in the interior layer innermost layer, can disperse mitigation to thrust power more effectively, blocks the propagation of the power of thrusting.The result can prevent penetration hole.

The present invention and then relate to a kind of Vacuum thermal insulating material, certain one deck by the laminating body that constitutes by plastic pellicle more than at least 2 layers and bonding layer break or layer with layer between the peeling off of some interfaces, can block and thrust the propagation of breaking that causes.Thrust the propagation of breaking that causes, by the layer a little less than the shear strength break or shear strength a little less than the peeling off of interface, can effectively disperse to relax and thrust the power of thrusting that layer is broken that causes coming, the propagation of power is thrust in blocking-up.The result can prevent to thrust the penetration hole that causes.

The present invention and then relate to a kind of Vacuum thermal insulating material, in the laminating body that is made of plastic pellicle more than at least 2 layers and their bonding layer of bonding, disrupted beds is an adhesive layer.

By the adhesive layer that uses in the laminated film is broken, can make harm rest on inferior limit to the functions such as blocked character of the necessity in the laminated film.And then, in the design of laminated film, owing to adhesive layer arbitrarily, can be designed on high-freedom degree ground so laminar structure is unrestricted as weak shear strength layer.

Common in addition, there are proportionate relationship in the Young's modulus of adhesive and the shear strength of adhesive, along with the decline shear strength of Young's modulus can step-down.By the adhesive of preferred use low elastic modulus, can reduce the shear strength of adhesive.Thereby, under the situation that foreign matter thrusts, because breaking appears in adhesive layer before running through laminated film, so can realize suppressing penetration hole by suppressing the propagation that foreign matter thrusts power.

The present invention and then relate to a kind of Vacuum thermal insulating material, its adhesive layer forms with polyurethane resin, and the Young's modulus of the plastic pellicle that modular ratio bondd of polyurethane resin is little.

Promptly, because the Young's modulus as the plastic pellicle that modular ratio bondd of the polyurethane resin of adhesive is little and soft, thereby outside the breaking through of inner foreign matter on the direction of packaging material under the situation of active force, can absorb this by bonding layer and be out of shape and suppress to cause producing pin hole by thrusting.

Usually, there are proportionate relationship in the Young's modulus of adhesive and the shear strength of adhesive, along with the decline shear strength of Young's modulus can reduce.Therefore, if reduce the shear strength of adhesive by the adhesive that uses low elastic modulus, then under the situation that foreign matter thrusts, breaking appears in bonding layer before the packaging material thrusting outside, so can realize suppressing pin hole by the propagation that the inhibition foreign matter thrusts power.

According to above result,, also can obtain to have the Vacuum thermal insulating material of excellent in resistance pin hole even in the core that has used staple glass fibre, sneaked under the situation of the such foreign matter of glass slag.

The present invention and then relate to a kind of Vacuum thermal insulating material, each interlayer of its laminating body at least one layer by layer between bonding be what to finish by the polyurethane resin that comprises polyisocyanates and polyester polyatomic alcohol polybasic alcohol.The equivalent proportion of polyisocyanates and polyester polyatomic alcohol polybasic alcohol is 1～3, and the polyurethane resin that is about to the polyisocyanates surplus is as bonding layer.

If by as the allophanate reaction of cross-linking reaction of the isocyanates that constitutes polyurethane resin or biuret reaction and then by the key that forms from isocyanuric acid ester reaction, carbodiimide reaction or urea alkane two reactive ketones etc. of addition reaction as isocyanates seldom, then polyurethane resin has elasticity and shows the such characteristic of thermoplastic resin.

The result is if that according to above-mentioned equivalent proportion, the polyurethane resin that constitutes bonding layer as can be known has the target Young's modulus.

The present invention and then relate to a kind of Vacuum thermal insulating material, outer packaging material is a laminating body, each interlayer of laminating body at least one layer by layer between bonding constitute by polyurethane resin and be to comprise the polyurethane resin of aliphatic category polyisocyanates as bonding layer.

In order to make polymeric compound have low elastic modulus, be necessary on chemical structure, to have filiform molecular structure to a certain degree, thereby isocyanate prepolymer composition becomes difunctional or is similar to difunctional.As the hexamethylene diisocyanate (HDI) of aliphatic category polyisocyanates, trimethyl hexamethylene diisocyanate (TMDI), LDI (LDI) etc. for realizing that low elastic modulus is effective especially.

By using these isocyanates, can reduce the Young's modulus of the polyurethane resin that constitutes bonding layer.

The present invention and then relate to and to contain the Vacuum thermal insulating material of the polyurethane resin of the pure and mild aliphatic category polyisocyanates of aliphatic category polyester polyols as bonding layer.

For polyol component,, can further reduce the Young's modulus of the polyurethane resin that constitutes bonding layer by using the aliphatic category polyester polyol.

The present invention and then relate to a kind of cold insulation equipment that uses in the following temperature province of normal temperature, in the outer container of cold insulation equipment and space that interior box-shaped becomes, filled in any one of the body of thermal insulating box of hard resin foam or insulated door, between interior case and outer container, possessed Vacuum thermal insulating material of the present invention.

Generally, as the plastics of polymeric compound, along with the reduction of temperature can lose ductility, hardening and becomes fragile, Young's modulus increases.Yet, constitute the bonding layer of the outer packaging material of the Vacuum thermal insulating material be applicable to cold insulation equipment owing to just had low elastic modulus originally, even thereby the temperature province below normal temperature use and also can keep sufficient ductility.

Therefore, for the cold insulation equipment that below normal temperature, uses, because the Young's modulus by packaging material that modular ratio bondd as the polyurethane resin of adhesive is little, even thereby under the situation of active force on the lateral direction of inner foreign matter packaging material outside breaking through, bonding layer also can absorb this distortion, thereby can suppress by the generation of thrusting the pin hole that causes.

In addition, the forming method of the laminating body adhesive that preferably uses dry lamination the to use dry lamination mode of carrying out.In addition, on the part of laminating body, can preferably use resin that olefine kind resin is melt extruded extrusion laminate mode as bonding layer.

During dry lamination, coating binder can use notch board coating machine (gravure coater) and reverse coating machine (reverse coater).The coating weight of adhesive (solid constituent) is generally 2～10g/m ², the laminated film behind the lamination is aging through 20～120 hours under 20～50 ℃ usually, and adhesive can solidify fully.

On the other hand, can be used for the viewpoint of core of the present invention, preferred glass fibers from heat-insulating property.In addition, staple glass fibre then can have special problem ground and uses so long as can Fibrotic glass composition.It is desirable to more, the aggregate of staple glass fibre is made of the lamina reticularis zoarium of staple glass fibre, comes combination by the interlacing of the required minimum of the integrality that can keep aggregate between net, on thickness direction equably the lamination assortment be preferred.And then, pin hole appears in order to suppress outer packaging material, more preferably there is not the staple glass fibre that the foreign matter of glass slag etc. is sneaked into.As the universal industrial goods that satisfy such condition, from the viewpoint of price and operability, more preferably glass wool.

In addition, though do not specify the fiber footpath, what the fiber footpath was thinner can obtain more excellent heat-insulating property.Yet from the viewpoint of Economy, preferably using average fiber directly is the glass fibre of 3～5 μ m.

The present invention and then relate to a kind of Vacuum thermal insulating material, in the laminating body that is made of plastic pellicle more than at least 2 layers and their bonding layer of bonding, disrupted beds is a plastic film layers.

By disrupted beds is made as plastic film layers, can make the thickness of weak shear strength layer compare thick a lot with the thickness of bonding layer.Therefore,, also can easily disperse to relax this and thrust power, also can guarantee sufficient anti-pin hole the foreign matter or the such big foreign matter of aspect ratio of fiber of large volume even make under the situation that foreign matter thrusts in brute force.

The present invention and then relate to a kind of Vacuum thermal insulating material in addition, in the laminating body that is made of plastic pellicle more than at least 2 layers and their bonding layer of bonding, the interface that peel off is the interface between any one of adhesive layer and plastic film layers, metal foil layer or evaporation layer.

By the interface peel of the adhesive layer that makes plastic film layers, metal foil layer or evaporation layer and be adjacent, can make harm rest on inferior limit to functions such as blocked character necessary in the laminated film.And then, when making laminated film, because shear strength layer a little less than can adhesive layer is made arbitrarily, thereby limiting layer laminated structure, high-freedom degree ground do not design.

The present invention and then relate to a kind of Vacuum thermal insulating material, in the laminating body that is made of plastic pellicle more than at least 2 layers and bonding layer, peeling off the interface is the interface of evaporation layer and evaporation base film layer.

By thrusting breaking of the laminated film that causes, by the interface peel in the interface a little less than the shear strength, the power of thrusting is disperseed to relax, so the propagation of breaking is blocked.

Particularly, under the situation of the shear strength in the interface of weakening evaporation layer and evaporation base film layer, can confirm to improve significantly to the such small foreign matter of glass fibre or the anti-pin hole of superfine dust.

In addition, in order to peel off at the interface that makes evaporation layer and evaporation base film layer, though can use the evaporated film of evaporating quality difference, under the situation of indispensable blocked character, can be by realizing in the surface coated of evaporation layer and the resin of the high adhesive force of vapor-deposited film in advance.

The present invention and then relate to a kind of Vacuum thermal insulating material in the laminating body that is made of plastic pellicle more than at least 2 layers and bonding layer, peels off the interface and is the thermal fusion welding interface of the plastic pellicle of making by co-extrusion.

By the plastic pellicle of co-extrusion making, a little less than the thermal fusion welding interface shear strength of plastic pellicle.This is because by a little less than the lamination strength at the interface between the plastic pellicle of thermal fusion welding.By using the plastic pellicle that adopts such co-extrusion to make, can improve anti-pin hole.

And then because co-extrusion film compares with the laminated film that utilizes dry lamination to make, advantage is big aspect cost, so by using co-extrusion film, can implement anti-pin hole countermeasure at low cost.

The present invention relates to a kind of Vacuum thermal insulating material in addition, in the laminating body that is made of plastic pellicle more than at least 2 layers and bonding layer, certain one deck in the laminating body or the shear strength at some interfaces are at 500N/cm ²Below.

By making shear strength be in 500N/cm ²Below, when being subjected to thrusting power, can genetic horizon break or layer between peel off.That is,, the power of thrusting can be effectively weakened, the downward Es-region propagations that breaks can be blocked by being in this below intensity.

The present invention and then relate to a kind of Vacuum thermal insulating material, in the laminating body that is made of plastic pellicle more than at least 2 layers and their bonding layer of bonding, the peeling strength at some interfaces of laminating body is below the 250N/m.

By making peeling strength is below the 250N/m, and the power of thrusting can easily cause to be peeled off, thereby can weaken the power of thrusting effectively.Under this situation below intensity, can block the downward Es-region propagations that breaks.

The laminated film that the outer packaging material of the formation that can use is in the present invention used in order to give high gas barrier property, more preferably has the plastics made membrane of the one deck in metal foil layer or the metal evaporation layer at least.At this moment, metal foil layer and metal evaporation layer for example can utilize material known such as aluminium, not special the appointment.

Below, specify example of the present invention with reference to accompanying drawing.In addition, can not limit the present invention with these examples.

(example 1)

Fig. 1 is the sectional drawing of the Vacuum thermal insulating material in the invention process form 1.In addition, Fig. 2 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the invention process form 1.

In Fig. 1, Vacuum thermal insulating material 11 is, insert core 12 and sorbent 14 in the packaging material 13 outside after, inner pressure relief forms.Concrete was, with core 12 in 140 ℃ baking oven dry 30 minutes.Utilize thermal fusion welding to seal the three parts of laminated film, outer packaging material 13 is shaped to a bag shape.Insert dry core 12 and sorbent 14 in the outer packaging material 13 of moulding, reducing pressure in the underpressure chamber reaches below the 13Pa until outer packaging material 13 inside, utilizes thermal fusion welding sealed open portion.

Outer packaging material 13 in the example 1, it is the laminating body that has following layer from inboard (being core 12 sides) beginning successively, promptly, by the thick linear low density polyethylene film of 50 μ m (below, be called for short the LLDPE film) the 2nd plastic film layers 24 that constitutes of the sealing layer 21 that constitutes, the metal foil layer 22 that constitutes by the thick aluminium foil of 6 μ m, the 1st plastic film layers 23 that constitutes by the thick polyethylene terephthalate thin film of 12 μ m (below, be called for short the PET film) and the thick nylon film of 25 μ m.

Sealing layer 21 herein is called as hot welding layer.

In addition, between each layer, use the adhesive that constitutes by polyurethane resin, and to utilize the dry lamination method to constitute laminated film be 3.5g/m until gluing dosage (solid constituent) as bonding layer 25,26 ²

In addition, between sealing layer 21 and the metal foil layer 22, between metal foil layer 22 and the 1st plastic film layers 23, the 1st adhesive layer that uses that known polyurethane tackifier constitutes is 25 gluing, making layer is fit.The shear strength that contains the laminating body of the 1st adhesive layer 25 is 1000N/cm ²

In addition, between the 1st plastic film layers 23 and the 2nd plastic film layers 24, the 2nd adhesive layer 26 that constitutes by the adhesive by low elastic modulus comes lamination.The shear strength that contains the laminating body of the 2nd adhesive layer 26 is 300N/cm ²During generally with the little adhesive lamination of Young's modulus, peeling strength becomes big on the one hand, and shear strength has the trend that diminishes on the other hand.

In addition, in the 2nd adhesive layer 26, use the aliphatic category dry lamination of big Japanese イ Application キ system to stick with glue agent デ _{The イ Star}Network De ラ イ LX-500/KR-90S, mixing ratio is LX-500:KR-90S=15:1.

On the other hand, core 12 is the net that is made of staple glass fibre laminating bodies through the glass fibre of interfibrous physical crosslinking be combined into.Use directly is the laminating body that the glass wool of 3.5 μ m is stacked to regulation density by average fiber.Be shaped to tabular in 5 minutes in 450 ℃ of following hot pressing also lower than glass heat deformation point.

Sorbent 14 for example, uses the calcium oxide as moisture adsorbent.

The Vacuum thermal insulating material 11 of Zhi Zuoing like this, the anti-pin hole of having distinguished outer packaging material 13 is compared significantly with goods in the past and has been improved.And the result who measures pyroconductivity is 0.0026W/mK.

Next, the reason of the property improvement of anti-the pin hole is described below.

Because outer packaging material inside is the low pressure of 13Pa, inside has been subjected to from atmospheric about 1kg/m ² Compressive stress.In core 12 under the situation of contained small foreign matter packaging material 13 outside thrust the inboard, mainly be compressed stress as the laminated film of outer packaging material 13.

Because the most inboard sealing layer 21 of outer packaging material is made of LLDPE, very soft, thrust foreign matter and run through easily.And then aluminium foil 22 only is 6 μ m, so foreign matter runs through easily owing to extremely thin.Because the 1st plastic pellicle 23 is made of PET, generally is difficult to be run through by foreign matter, but can partly runs through.

Under the anterior thick situation of foreign matter, outer packaging material mainly was subjected to tensile stress when pressure was paid foreign matter, but under the anterior thin situation of foreign matter, outer packaging material mainly is compressed stress.

Thrust the foreign matter pressure and pay when the 1st plastic film layers 23, the 1st plastic film layers 23 is compressed at the thorn Inbound.When breaking, power is that the center discharges laterally with the foreign matter, and this power attempts to propagate to the 2nd plastic pellicle 24.

Yet, between the 1st plastic pellicle 23 and the 2nd plastic pellicle 24, have the 2nd adhesive layer 26 of weak shear strength.Because shear action breaks in the 2nd adhesive layer 26, the 2 adhesive layers 26, relax and reduced the power of thrusting.Breaking of the 1st plastic pellicle 23 do not propagate in the 2nd plastic pellicle 24 as a result.So, can prevent that penetration hole from appearring in outer packaging material.

If further the viewpoint from material illustrates, the 2nd adhesive layer 26 that uses between the 1st plastic pellicle 23 and the 2nd plastic pellicle 24 uses polyurethane resin adhesive layer, that contain the pure and mild aliphatic category polyisocyanates of aliphatic category polyester polyols as weak shear strength.

The Young's modulus of general adhesive and the proportional relation of shear strength of adhesive are along with the decline shear strength reduction of Young's modulus.Therefore can think, under the situation that foreign matter thrusts,, relax and weakened the power of thrusting, thereby block foreign matter and thrust the propagation of power, pin hole occur thereby can be suppressed in the more topmost thin film of weak adhesive layer because the weak adhesive layer of shear strength breaks.

As mentioned above, can guarantee as the sufficient gas barrier property of the outer packaging material of Vacuum thermal insulating material and have the outer packaging material that the laminated film of excellent anti-pin hole constitutes by being equipped with, can be provided at the high-quality Vacuum thermal insulating material that has excellent heat-insulating property in long-time.

In addition, to the Vacuum thermal insulating material of making, measure its pyroconductivity after the week in form 1 of the present invention, the result is 0.0026W/mK, does not find that pyroconductivity worsens.Therefore can judge, in a Vacuum thermal insulating material, all not produce penetration hole.

In addition, have weak shear strength in order to make bonding layer, adhesive is necessary to have linear molecule structure to a certain degree on chemical structure.Therefore isocyanate prepolymer composition preferably has 2 functional groups or is similar to the straight chain structure of 2 functional groups.

Therefore, in order to realize low elastic modulus, effective especially as the hexamethylene diisocyanate (HDI) of aliphatic category polyisocyanates, trimethyl hexamethylene diisocyanate (TMDI), LDI (LDI) etc.

In addition, reduction also is effective as the crosslink density of the polyurethane resin of adhesive material.Therefore, the equivalent proportion of preferred polyisocyanates and polyatomic alcohol polybasic alcohol is 1～3, is more preferably the polyurethane resin of 1～2 polyisocyanates surplus.That is, the cooperation of the preferred mixing ratio manufacturer recommendation of isocyanate prepolymer composition also reduces by 10～30wt%.By using such isocyanates, can reduce the Young's modulus of the polyurethane resin that constitutes adhesive layer, reduce shear strength.

In addition, the shear strength of laminating body that contains bonding layer is low more, and is effective more to improving anti-pin hole, but then, if shear strength is 100N/cm ²Below, when the operations such as outer packaging material through firmly bending Vacuum thermal insulating material make laminated film be subjected to loading, cause peeling off of laminated film easily by shearing.Therefore, preferred shear strength is 100～300N/cm ², preferred especially shear strength is 100～200N/cm ²

Be used for outer packaging material by the laminating body that will have such shear strength, the high-quality Vacuum thermal insulating material that fully satisfies anti-pin hole and other rerum natura can be provided.

For the mensuration of the shear strength of laminating body among the present invention,, can measure according to the test method of JISK6850 as 1 example.An example of concrete determining method has been shown among Fig. 3.In Fig. 3, show the 1st plastic pellicle 23 and the 2nd plastic pellicle 24 test film by the gluing laminating body of the 2nd adhesive layer 26 of weak shear strength.Wait and make test film by pasting sheet metal 30 on as the outermost surface film of the laminating body of determination object.Fig. 3 shows the test film of pasting sheet metal 30 on the 1st plastic film layers 23 and the 2nd plastic film layers 24.Two end portions by controlling test film, on the left and right directions of Fig. 3, carry out tension test, can measure the layer of inside of laminating body or the tensile shear strength at the interface between interior layer and the layer.

(example 2)

Fig. 4 is the sectional drawing of the outer packaging material of this example 2.

As shown in Figure 4, the outer packaging material 13 of this example is the laminating body that comprises successively from the inboard with lower floor, that is the 2nd plastic film layers 24 that the nylon film that the 1st plastic film layers 23 that the PET film that sealing layer 21, the 12 μ m that the LLDPE film that, 50 μ m are thick constitutes are thick constitutes and 25 μ m are thick constitutes.

In addition, the 1st plastic film layers 23 has evaporation layer 27 on the face relative with the 2nd plastic film layers 24 sides.Vapor-deposited film is an AM aluminum metallization to 500

Thick form.

Between sealing layer 21 and the 1st plastic film layers 23, and the 1st plastic film layers 23 and the 2nd plastic film layers 24 between, the 1st adhesive layer 25 is set respectively, come laminated with known method by dry lamination.Use known polyurethane tackifier as the 1st adhesive layer 25.

In addition, the Vacuum thermal insulating material of the form 2 of this enforcement beyond the material formation difference of packaging material 13, uses the method identical with the making method of example 1 to make.

The laminated film of Zhi Zuoing like this, the shear strength of the laminating body that is made of sealing layer 21 and the 1st plastic film layers 23 is 1000N/cm ²

On the other hand, the shear strength of the laminating body of the 1st plastic film layers 23 and the 2nd plastic film layers 24 formations is 250N/cm ²After measuring the shear strength of laminating body, confirmed that the interface between the 1st plastic film layers 23 and the evaporation layer 27 is peeled off.

The Vacuum thermal insulating material of making like this 11 compares with product in the past, can distinguish that the anti-pin hole of outer packaging material 13 is significantly improved.In addition, the result of mensuration pyroconductivity is 0.0025W/mK.

Below the key reason that improves anti-pin hole is described.The 1st plastic film layers 23 is subjected to that foreign matter brings when thrusting power, and the 1st plastic pellicle 23 is compressed, and is extended on the direction vertical with the thorn Inbound.Therefore to the 2nd plastic pellicle 24 from the tensile force that thrust the central point effect.

Yet the shear strength of the laminating body that is made of the 1st plastic film layers 23, evaporation layer the 27, the 1st adhesive layer 25 and the 2nd plastic film layers 24 is little, is 250N/cm ²This can think to have weakened the power of thrusting because shear action in evaporation layer 27, is peeled off at the interface of the 1st plastic film layers 23 and evaporation layer 27 thereby relax.Thus, breaking of the 1st plastic film layers 23 do not propagated to the 2nd plastic film layers 24.Thereby, can prevent to produce penetration hole on the outer packaging material.

Go up according to this result, can guarantee as the sufficient gas barrier property of the outer packaging material of Vacuum thermal insulating material and have the outer packaging material that the laminated film of excellent anti-pin hole constitutes by being equipped with, can be provided at the high-quality Vacuum thermal insulating material that has excellent heat-insulating property in long-time.

In addition, for the shear strength at the interface that reduces evaporation layer and evaporation base film layer, also can realize by the evaporated film that uses the evaporating quality difference.Yet need under the situation of gas barrier property preferred coating and the high resin of vapor-deposited film adhesive force on the surface of evaporation layer in advance.

As the resin high, can use the known gluing material of using with the vapor-deposited film adhesive force.As an example, if vapor-deposited film is an aluminium, then polyacrylic acid analog copolymer and polyalcohols mixture of polymers are effective.

More preferably, behind coating mixture, under about 200 ℃, heat-treat, like this when further increasing the adhesive quality of vapor-deposited film and coating mixture, because the thermal expansion of base film causes the combination force of base film and vapor-deposited film to weaken, thus preferred.

In addition, in the form 2 of this enforcement, use the aluminium-vapour deposition layer, even but use ceramic evaporation layer instead and also can obtain same result as the evaporation layer.

(example 3)

Fig. 5 is the sectional drawing of the outer packaging material in the example 3 of the present invention.

As shown in Figure 5, outer packaging material 13 is the laminating bodies that contain following layer from the inboard successively, that is the 2nd plastic film layers 24 that the nylon film that the 1st plastic film layers 23 that the nylon film that metal foil layer 22, the 15 μ m that the aluminium foil that sealing layer 21, the 6 μ m that the LLDPE film that, 50 μ m are thick constitutes are thick constitutes are thick constitutes and 25 μ m are thick constitutes.

And then, form as laminated co-extrusion film layer 28 by co-extrusion the 1st plastic film layers 23 and the 2nd plastic film layers 24.

In addition, between sealing layer 21 and the metal foil layer 22 and between metal foil layer 22 and the 1st plastic film layers 23, use the 1st adhesive layer 25 that constitutes by known polyurethane tackifier gluing.

In addition, the making method of the Vacuum thermal insulating material in this example, beyond the material formation difference of packaging material 13, all the other are identical with example 1.

In the laminated film of making like this, the shear strength of the laminating body that is made of sealing layer 21, metal foil layer the 22, the 1st plastic film layers 23 and the 1st adhesive layer 25 is 1000N/cm ²

On the other hand, the shear strength of the laminating body of the 1st plastic film layers 23 and the 2nd plastic film layers 24 formations is 150N/cm ²After the shear strength of measuring laminating body, confirmed that the interface of the 1st plastic film layers 23 and the 2nd plastic film layers 24 is peeled off.

The Vacuum thermal insulating material 11 of Zhi Zuoing like this, with in the past product relatively, the anti-pin hole of outer as can be known packaging material 13 has obtained significantly improvement.The result who measures pyroconductivity in addition is 0.0025W/mK.

Below the improved reason of anti-pin hole is described.When thrusting foreign matter and press to pay in the 1st plastic pellicle 23, the 1st plastic pellicle 23 is compressed on the thorn Inbound.Power therefrom discharges in the mind-set outside when breaking, and this power attempts to propagate to the 2nd plastic pellicle.

Yet the shear strength of the laminating body that the 1st plastic film layers 23 and the 2nd plastic film layers 24 constitute is little, is 150N/cm ², can think like this, at shear action during in the 1st plastic pellicle 23, owing to peel off on the interface of the 1st plastic film layers 23 and the 2nd plastic film layers 24, thereby mitigation has weakened the power of thrusting.As this result, can think to make breaking of the 1st plastic pellicle 23 not propagate to the 2nd plastic pellicle 24.Thereby can prevent that outer packaging material from producing penetration hole.

Go up according to this result, can guarantee as the sufficient gas barrier property of the outer packaging material of Vacuum thermal insulating material and have the outer packaging material that the laminated film of excellent anti-pin hole constitutes by being equipped with, can be provided at the high-quality Vacuum thermal insulating material that has excellent heat-insulating property in long-time.

(example 4)

Fig. 6 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 4 of the present invention.

As shown in Figure 6, outer packaging material 13 is the laminating bodies that have following layer from the inboard successively, that is the 2nd plastic film layers 24 that the nylon film that the 1st plastic film layers 29 that the ethylene-vinyl alcohol copolymer resin film that metal foil layer 22, the 12 μ m that the aluminium foil that sealing layer 21, the 6 μ m that the LLDPE film that, 50 μ m are thick constitutes are thick constitutes are thick constitutes and 25 μ m are thick constitutes.

Between sealing layer 21 and the metal foil layer 22, between metal foil layer 22 and the 1st plastic film layers 29 and between the 1st plastic film layers 29 and the 2nd plastic film layers 24, use the 1st adhesive layer 25 gluing respectively.As the 1st adhesive layer 25, use known polyurethane tackifier, come the outer packaging material 13 of laminated making by dry lamination as known method.

On the other hand, use ethylene-vinyl alcohol copolymer resin film (12 μ m) as the 1st plastic film layers 29, this resin utilizes as the plastic film layers with weak shear strength interface.

In addition, the Vacuum thermal insulating material of this example, beyond the material of packaging material 13 constituted difference, all the other were identical with making method in the example 1.

In the laminated film of making like this, the shear strength that contains the laminating body of the 1st plastic film layers 29 is 300N/cm ²After measuring the shear strength of laminating body, the interface of having confirmed the 1st plastic film layers 29 is peeled off and 29 generations of the 1st plastic film layers self are broken.

In addition, distinguished that the anti-pin hole and the product in the past of the outer packaging material 13 of Vacuum thermal insulating material 11 compares, obtained significantly improving.Pyroconductivity is 0.0025W/mK in addition.

The improved mechanism of anti-like this pin hole with above-mentioned same, is destroyed by the shearing force of bringing from the power of thrusting of inside by weak shear strength layer, weakens the power of thrusting thereby relax, and can prevent to produce penetration hole by the propagation that blocking-up is broken.

In this example, the 1st plastic film layers 29 can think that plastic film layers as weak shear strength works.

In addition, as the plastic pellicle of weak shear strength, be not limited to ethylene-vinyl alcohol copolymer resin film.Can be suitable for materials such as nylon film, polyethylene terephthalate thin film, polypropylene film and polyethylene film.

Go up according to this result, can guarantee as the sufficient gas barrier property of the outer packaging material of Vacuum thermal insulating material and have the outer packaging material that the laminated film of excellent anti-pin hole constitutes by being equipped with, can be provided at the high-quality Vacuum thermal insulating material that has excellent heat-insulating property in long-time.

(example 5)

Fig. 7 is the sectional drawing of the outer packaging material of example 5 of the present invention.

As shown in Figure 7, the outer packaging material 13 of this example is the laminating body that contains following layer from the inboard successively, that is the 2nd plastic film layers 44 that the nylon film that the 1st plastic film layers 43 that the PET film that metal foil layer 42, the 12 μ m that the aluminium foil that sealing layer 41, the 6 μ m that the LLDPE film that, 50 μ m are thick constitutes are thick constitutes are thick constitutes and 25 μ m are thick constitutes.

This laminated film has weak peeling strength interface 45 respectively in the interface of the interface of the 1st plastic film layers 43 and adhesive layer 46 and the 2nd plastic film layers 44 and adhesive layer 46.

In addition, the Vacuum thermal insulating material of this example, beyond the material of packaging material 13 constituted difference, all the other used the method identical with making method in the example 1 to make.

In addition, between sealing layer 41 and the metal foil 42 and between metal foil 42 and the 1st plastic film layers 43, use known polyurethane tackifier, it is gluing to utilize known dry lamination method, and the mutual peeling strength of each film is respectively more than 700N/m.

In addition, weak peeling strength interface 45 forms by between the 1st plastic pellicle 43 and the 2nd plastic pellicle 44 adhesive layer 46 being formed trellis.The area of paying of the adhesive by making trellis accounts for about 1/10 of whole gluing surfaces and is coated with like that, has weakened the adhesive strength of the 1st plastic pellicle 43 and the 2nd plastic pellicle 44.The peeling strength of this moment is 150N/m.

Distinguish that the anti-pin hole of the outer packaging material 13 of the Vacuum thermal insulating material 11 of Zhi Zuoing and product have in the past relatively obtained significantly improving like this.Measured pyroconductivity in addition, the result is 0.0026W/mK.

Below the improved mechanism of anti-pin hole in this example 5 is described.In core 12 under the situation of contained small foreign matter packaging material outside thrust the inboard, mainly be compressed stress as the laminated film of outer packaging material 13.Thrust foreign matter when the 1st plastic pellicle 43 pressures are paid, the 1st plastic pellicle 43 is compressed at the thorn Inbound.When breaking, power discharges laterally from thrusting central point, and this power attempts to propagate to the 2nd plastic pellicle 44.

Yet, between the 1st plastic pellicle 43 and the 2nd plastic pellicle 44, be provided with weak peeling strength interface 45.Be somebody's turn to do weak peeling strength interface when being compressed stress, peel off at the interface, thrusts the stress that brings thereby relax to have reduced.Therefore breaking of the 1st plastic pellicle 43 can not be propagated to the 2nd plastic pellicle 44.Like this, can prevent that outer packaging material from producing penetration hole.

In addition, in this example, the area of paying of the adhesive by making trellis accounts for about 1/10 of whole gluing surfaces and is coated with like that, thus the weak peeling strength interface that the moulding adhesive strength weakens.Except controlling gluing area, also can form weak peeling strength interface by the adhesive strength of controlling adhesive.

In addition, the peeling strength of laminating body that contains adhesive layer is weak more, and is effective more to improving anti-pin hole.Yet under the situation of peeling strength, at the outer packaging material of the tortuous Vacuum thermal insulating material of brute force etc., when making laminated film be subjected to loading, cause peeling off of laminated film easily by shearing less than 20N/m.Therefore, preferred peeling strength is more than 20～below the 200N/m, the peeling strength that is more preferably is more than 20～and below the 100N/m.

By the outer packaging material that use has such peeling strength, can provide the high-quality Vacuum thermal insulating material that fully satisfies anti-pin hole and other necessary rerum natura.

In addition, the structure of the adhesive layer 46 in this example 5 gets final product so long as adhesive almost is coated on the entire area equably, is not limited to trellis.It for example also can be cellular, round point shape etc.

(example 6)

Fig. 8 is the sectional drawing of the outer packaging material of example 6 of the present invention.

As shown in Figure 8, the outer packaging material 13 of this example is the laminating body that has following layer from the inboard successively, that is the 2nd plastic film layers 44 that the nylon film that the 1st plastic film layers 43 that the PET film that sealing layer 41, the 12 μ m that the LLDPE film that, 50 μ m are thick constitutes are thick constitutes and 25 μ m are thick constitutes.

In addition, on face on the 1st plastic film layers 43, relative with the 2nd plastic film layers 44, has evaporation layer 47.Evaporation layer 47 is to have implemented AM aluminum metallization to 500

Thick layer.On the interface of this evaporation layer 47 and the 1st plastic film layers 43, be provided with weak peeling strength interface 45.

In addition, the making method of the Vacuum thermal insulating material in this example, beyond the constituent material difference of packaging material 13, all the other are identical with making method in the example 1.

In addition, between sealing layer 41 and the 1st plastic film layers 43, between the 1st plastic film layers 43 and the 2nd plastic film layers 44, use known polyurethane tackifier, it is gluing to utilize known dry lamination method, and the mutual peeling strength of each film is respectively more than 700N/m.

In addition, weak peeling strength interface 45 be the 1st plastic pellicle 43 and. and the interface between the evaporation layer 47, peeling strength is 200N/m.

The anti-pin hole of outer packaging material 13 of having distinguished the Vacuum thermal insulating material 11 of such making has relatively obtained significantly improving with in the past product.In addition, measured pyroconductivity, the result is 0.0025W/mK.

The following describes the improved mechanism of anti-like this pin hole.Under the situation of contained small foreign matter packaging material outside thrust the inboard, outer packaging material 13 mainly is compressed stress in core 12.Thrusting foreign matter when the 1st plastic pellicle 43 pressures are paid, the 1st plastic pellicle 43 is compressed at the thorn Inbound.The Shi Licong that the breaks center of thrusting discharges laterally, and this power attempts to propagate to evaporation layer 47.

Yet, between the 1st plastic pellicle 43 and evaporation layer 47, be provided with weak peeling strength interface 45.During the peeling strength interface, peel off at the interface a little less than compressive stress acts on this, has weakened the power of bringing of thrusting thereby relax.Therefore breaking of the 1st plastic pellicle 43 do not propagated to the 2nd plastic pellicle 44.

Thus, can prevent outer packaging material generation penetration hole.

In addition, the reduction of the shear strength at the interface between evaporation layer and the evaporation base film layer can realize by the evaporated film that uses the evaporating quality difference.And then, under the situation of necessary blocked character, preferred coating and the high resin of vapor-deposited film adhesive force on the surface of evaporation layer in advance.

As the resin high with the vapor-deposited film adhesive force, can suitably use material known such as polyurethane resin, give one example, if vapor-deposited film is an aluminium, then polyacrylic acid analog copolymer and polyalcohols mixture of polymers are effective.In addition, can use the polymethacrylic acid copolymer to replace the polyacrylic acid analog copolymer.

More preferably, behind coating mixture, about 200 ℃, heat-treat, because when further increasing the adhesive quality of vapor-deposited film and coating layer, the thermal expansion of base film causes that the combination force of base film and vapor-deposited film weakens, thereby preferred.

(example 7)

Fig. 9 is the sectional drawing of the outer packaging material in the example 7 of the present invention.

As shown in Figure 9, outer packaging material 13 is the laminating bodies that have following layer from the inboard successively, that is the 2nd plastic film layers 44 that thin the 1st plastic film layers 43 that constitutes of the nylon membrane that metal foil layer 42, the 25 μ m that the aluminium foil that sealing layer 41, the 6 μ m that the LLDPE film that, 50 μ m are thick constitutes are thick constitutes are thick and the thick nylon film of 15 μ m constitute.

And then the 1st plastic film layers 43 and the 2nd plastic film layers 44 are by the laminated formation co-extrusion film of co-extrusion layer 48.

In this example 7, a little less than peel off the interface that interface 45 is the 1st plastic film layers 43 and the 2nd plastic film layers 44.

In addition, the making method of the Vacuum thermal insulating material in this example, beyond the constituent material difference of packaging material 13, all the other are identical with making method in the example 1.

Between sealing layer 41 and the metal foil 42 and between metal foil 42 and the 1st plastic film layers 43, it is gluing to use known polyurethane tackifier to utilize known dry lamination method in addition.The mutual peeling strength of each film is respectively more than 700N/m.

On the other hand, the peeling strength at weak peeling strength interface 45 is 100N/m.

Distinguished such making Vacuum thermal insulating material 11 outer packaging material 13 anti-pin hole and in the past product relatively, obtained significantly improving.Measured pyroconductivity in addition, the result is 0.0025W/mK.

The following describes the improved mechanism of anti-like this pin hole.In core 12 under the situation of contained small foreign matter packaging material outside thrust the inboard, mainly be compressed stress as the laminated film of outer packaging material 13.Thrusting foreign matter when the 1st plastic pellicle 43 pressures are paid, the 1st plastic pellicle 43 is compressed at the thorn Inbound, and power therefrom discharges in the mind-set outside when breaking, and this power is attempted to 44 propagation of the 2nd plastic pellicle.

Yet between the 1st plastic pellicle 43 and the 2nd plastic pellicle 44, be provided with weak peeling strength interface 45.Thrusting the stress that brings a little less than this during the peeling strength interface, peel off at the interface.The result is weakened by mitigation owing to the power of thrusting, so breaking of the 1st plastic pellicle 43 propagated to the 2nd plastic pellicle 44.

Thus, can prevent that outer packaging material from producing penetration hole.

(example 8)

Figure 10 is the sectional drawing of the outer packaging material of the Vacuum thermal insulating material in the example 8 of the present invention.

The making of Vacuum thermal insulating material 11 adopts the method identical with example 1 to carry out.

At this moment, outer packaging material 13 is the laminating bodies that have following layer from the inboard successively, that is the 2nd plastic film layers 24 that thin the 1st plastic film layers 23 that constitutes of the nylon membrane that metal foil 22, the 25 μ m that the aluminium foil that sealing layer 21, the 6 μ m that the LLDPE film that, 50 μ m are thick constitutes are thick constitutes are thick and the thick nylon film of 15 μ m constitute.In addition, be provided with the bonding layer 26 that constitutes by polyurethane resin, be used for the gluing of each interlayer at each interlayer of laminating body.

Laminating body is to make the gluing dosage (solid constituent) of bonding layer 26 reach 3.5g/m ²Like that, utilize the dry lamination method to make.

In addition, the polyurethane resin of bonding layer 26, the adhesive デ that uses the dry lamination of the aliphatic category of big Japanese イ Application キ system to use _{The イ Star}Network De ラ イ LX-500/KR-90S, mixing ratio is LX-500:KR-90S=15:1.

In addition, the making method of the Vacuum thermal insulating material in this example 8, beyond the constituent material difference of packaging material 13, all the other are identical with making method in the example 1.

Distinguish that the Vacuum thermal insulating material of Zhi Zuoing like this, the anti-pin hole of outer packaging material and product have in the past relatively obtained significantly improving.

Owing to used the polyurethane resin that contains the pure and mild aliphatic category polyisocyanates of aliphatic category polyester polyols as adhesive, thereby the polyurethane resin of bonding layer is low elastic modulus, and has the ductility of appropriateness.Its result, can think, the direction of packaging material applies under the situation of active force outside little, the inner foreign matter of the gluing Young's modulus by adhesive material of the modular ratio of polyurethane resin is being broken through, and absorbs this distortion by bonding layer, can suppress to thrust the generation of the pin hole that causes.

And then, the Young's modulus of adhesive and the proportional relation of the shear strength of adhesive, usually, along with the decline shear strength of Young's modulus can reduce.Thereby can think that thrust at foreign matter under the situation of sealing layer, because after running through sealing layer, the weak bonding layer of shear strength breaks, therefore having suppressed foreign matter thrusts the propagation of power, thereby can suppress the film generation pin hole on upper strata more.

(example 9)

Figure 11 is the sectional drawing that has used the deep freezer of the Vacuum thermal insulating material in the example 8 of the present invention.As an example of cold insulation equipment, the situation of deep freezer is described below.

As shown in figure 11, refrigerator 51 is made of the body of thermal insulating box 52 and the freeze cycle that form the refrigerator framework.Body of thermal insulating box is that the interior case 54 by moulding such as the outer container 53 of iron plate compression and moulding and ABS resin assembles via flange (not shown).In the inside of body of thermal insulating box 52, be equipped with Vacuum thermal insulating material 11 in advance.Space segment beyond Vacuum thermal insulating material 11 is filled with RPUF (hard resin foamed plastics) 55.When making RPUF 55, use cyclopentane as stabilizer.

Body of thermal insulating box 52 is separated by dividing plate 56, and top is cold storage room 57, and the bottom is a refrigerating chamber 58.Electric-power damper 59 has been installed on dividing plate 56, in the interior case 54 of refrigerating chamber 58, the fan electromotor 60 and the defrosting heater 61 of cooling usefulness has been installed.

On the other hand, freeze cycle is made of vaporizer 62, compressor 63, condenser 64, capillary tube 65 etc., and connects with this order ring-type and to form.In addition, vaporizer 62 can be arranged on cold storage room 57 and refrigerating chamber 58 these two positions, they serial or parallel connections can be connected to form freeze cycle.

In addition, door 66 has been installed on refrigerator 51, has been equipped with Vacuum thermal insulating material 11 in the inside of door 66, the space beyond Vacuum thermal insulating material is filled with RPUF 55.

Vacuum thermal insulating material 11 in addition, can use the Vacuum thermal insulating material shown in the example 8.

As the plastics of polymeric compound, generally the reduction along with temperature can lose the ductility hardening, and becomes fragile, and Young's modulus increases.Yet, constitute the polyurethane resin of bonding layer 26 of the outer packaging material of the Vacuum thermal insulating material 11 be applicable to refrigerator 51 owing to be exactly low elastic modulus originally, even thereby the temperature province below normal temperature use and also can keep sufficient ductility.

Therefore, even use the temperature province about from normal temperature to refrigerator temperature in the cabinet-18 ℃ under the situation of Vacuum thermal insulating material, because the Young's modulus of the polyurethane resin of formation bonding layer is little, the Young's modulus by adhesive material gluing as the modular ratio of the polyurethane resin of adhesive is little, so under the situation of the outer packaging material side active force of breakthrough laminate structures, can absorb this by bonding layer and be out of shape the generation that suppresses to thrust the pin hole that causes at inner foreign matter.

Its result, the quality of the Vacuum thermal insulating material of this example can be stablized maintenance in long-time, used the refrigerator of this example of above-mentioned Vacuum thermal insulating material, can keep the effect that reduces consumes power in long-time.

And then, from keeping the viewpoint of Young's modulus, the equal temperature of the temperature province of the vitrifying point of the polyurethane resin of the bonding layer 26 of outer packaging material and suitable Vacuum thermal insulating material or this is below temperature more preferably.

Below, come the polyurethane resin of the bonding layer of external packaging material to be specifically described with embodiment and comparative example.In addition, the present invention is not limited in these embodiments.

In table 1, show embodiment 1～4 and Comparative examples A～D, the adhesive to dry lamination the time carries out the anti-pin hole of the Vacuum thermal insulating material under the situation of all changes.

Table 1

The basic method identical with example 8 of Vacuum thermal insulating material 11 usefulness made, and only the material of the bonding layer 26 of the outer packaging material 13 of formation Vacuum thermal insulating material 11 carried out various changes and makes.In addition, in order to confirm the anti-pin hole of Vacuum thermal insulating material 11, only the glass slag that is adjusted to certain particle diameter in advance of established amount is being configured under the state on core surface, reduced pressure sealing is made Vacuum thermal insulating material 11.To the gas leakage that has or not Vacuum thermal insulating material behind the reduced pressure sealing and outside the folding test of Vacuum thermal insulating material has or not peeling off of packaging material estimate.

In addition, table 1 also shows the rerum natura of the polyurethane resin that constitutes bonding layer 26 simultaneously.Comparison for Young's modulus, the Young's modulus of polyurethane resin of bonding layer 26 and film etc. have been compared by the Young's modulus of adhesive material, for surface hardness, made the body polyurethane resin, utilize durometer under 20 ℃ and 0 ℃, to measure this surface hardness.In addition, though surface hardness is estimated as the replacement rerum natura of Young's modulus,, can use tensile modulus of elasticity and modulus of elasticity in comperssion etc. as Young's modulus.

In addition, in Vacuum thermal insulating material 11, except the Vacuum thermal insulating material shown in the example 8, can use the Vacuum thermal insulating material described in the example 1～7.

(embodiment 1)

Constituting the polyurethane resin of bonding layer 26 shown in Figure 10, is the polyurethane resin that contains the modification body of the pure and mild hexamethylene diisocyanate as the aliphatic category polyisocyanates of aliphatic category polyester polyols (HDI).

The Young's modulus of the polyurethane resin of bonding layer 26 is littler than the Young's modulus of each film that constitutes outer packaging material 13 at this moment.In addition, the surface hardness of polyurethane resin, lower under 20 ℃, be 40, and 20 ℃ and 0 ℃ of surface hardness indifference.

There is not problems such as producing peeling off of pin hole and outer packaging material in the Vacuum thermal insulating material that comprises above-mentioned formation.

In addition, as the aliphatic category polyisocyanates, can use known aliphatic category polyisocyanates, but preferably use hexamethylene diisocyanate (HDI), trimethyl hexamethylene diisocyanate (TMDI), LDI (LDI) etc., be more preferably the modification body of these vulcabond.

As the aliphatic category polyester polyol, can preferably use known aliphatic category polyester polyol equally.

(embodiment 2)

Bonding layer 26 among Figure 10 is to make of the polyurethane resin of the modification body that contains the pure and mild IPDI as alicyclic ring shape kind isocyanate of aliphatic category polyester polyols (IPDI).The equivalent proportion that its cooperation ratio is polyisocyanates and polyatomic alcohol polybasic alcohol is 2, and polyisocyanates is excessive.

At this moment, the Young's modulus of each film of the outer packaging material 13 of the modular ratio of the polyurethane resin of bonding layer 26 formation is all little.In addition, the surface hardness of polyurethane resin at 20 ℃ lower, is 40, and in the surface hardness indifference of 20 ℃ and 0 ℃.

There is not problems such as producing peeling off of pin hole and outer packaging material in the Vacuum thermal insulating material that comprises above-mentioned formation.

In addition, under the situation that can not be suitable for the aliphatic category isocyanates, suitably using alicyclic ring shape kind isocyanate is effectively, and in this case, the equivalent proportion of preferred polyisocyanates and polyatomic alcohol polybasic alcohol is 1～3, the polyisocyanates surplus.

As alicyclic ring shape isocyanates, can preferably use known, for example, dicyclohexyl methyl hydride diisocyanate (HMDI), different phorone vulcabond (IPDI), 1,4-cyclohexane diisocyanate (CHDI) etc.

In addition, the equivalent proportion of preferred polyisocyanates and polyatomic alcohol polybasic alcohol is 1～3, and polyisocyanates surplus, the equivalent proportion that is more preferably are 1～2.In addition, under the polyurethane resin state of bonding layer 26, in order to judge equivalent proportion, for example can be by measuring infrared absorption spectroscopy, the absorption intensity that many isocyanates cause is judged.

(embodiment 3)

Bonding layer 26 is to make of the polyurethane resin of the modification body that contains the pure and mild dicyclohexyl methyl hydride diisocyanate as alicyclic ring shape kind isocyanate of aliphatic category polyester polyols (HMDI).The equivalent proportion that its cooperation ratio is polyisocyanates and polyatomic alcohol polybasic alcohol is 2, and polyisocyanates is excessive.

At this moment, the Young's modulus of each film of the outer packaging material 13 of the modular ratio of the polyurethane resin of bonding layer 26 formation is all little.In addition, the surface hardness of polyurethane resin is 45 (20 ℃), 46 (0 ℃).

There is not problems such as producing peeling off of pin hole and outer packaging material in the Vacuum thermal insulating material that comprises said structure.

(embodiment 4)

Bonding layer 26 is to make of the polyurethane resin of the performed polymer that contains the pure and mild toluene di-isocyanate(TDI) of aliphatic category polyester polyols (TDI).The equivalent proportion that its cooperation ratio is polyisocyanates and polyatomic alcohol polybasic alcohol is 2, and polyisocyanates is excessive.

At this moment, the Young's modulus of each film of the outer packaging material 13 of the modular ratio of the polyurethane resin of bonding layer 26 formation is all little.In addition, the surface hardness of polyurethane resin is 45 (20 ℃), 46 (0 ℃).

There is not problems such as producing peeling off of pin hole and outer packaging material in the Vacuum thermal insulating material that comprises said structure.

(Comparative examples A)

Bonding layer 26 is to make of the polyurethane resin of the performed polymer that contains the pure and mild toluene di-isocyanate(TDI) of aliphatic category polyester polyols (TDI).The equivalent proportion that its cooperation ratio is polyisocyanates and polyatomic alcohol polybasic alcohol is 3.2, and polyisocyanates is excessive.

At this moment, the Young's modulus of each film of the outer packaging material 13 of the modular ratio of the polyurethane resin of bonding layer 26 formation is all little.In addition, 20 ℃ surface hardness of polyurethane resin is 50, and than the polyurethane resin height shown in the embodiment, and the difference of the surface hardness of 20 ℃ and 0 ℃ is 5.

The Vacuum thermal insulating material that comprises said structure although outer packaging material is peeled off, produces a large amount of pin holes, and breaks.

Like this, surpass at 3 o'clock, can think because the degree of cross linking of polyurethane resin increases, so cause polyurethane resin to follow the string in the equivalent proportion of polyisocyanates and polyatomic alcohol polybasic alcohol.

(comparative example B)

Bonding layer 26 is to make of the polyurethane resin of the performed polymer that contains the pure and mild toluene di-isocyanate(TDI) of aliphatic category polyester polyols (TDI).The equivalent proportion that its cooperation ratio is polyisocyanates and polyatomic alcohol polybasic alcohol is 0.9, and polyisocyanates is few.

At this moment, the Young's modulus of each film of the outer packaging material 13 of the modular ratio of the polyurethane resin of bonding layer 26 formation is all little.In addition, the surface hardness of polyurethane resin is 45, with the polyurethane resin shown in the embodiment substantially in identical level, and the difference of the surface hardness of 20 ℃ and 0 ℃ is 1.

The Vacuum thermal insulating material that comprises said structure does not produce pin hole.But through the folding test of Vacuum thermal insulating material, the part between outer packaging material thin layer is peeled off.

(comparative example C)

The polyurethane resin that constitutes bonding layer 26 is the polyurethane resin that contains the pure and mild toluene di-isocyanate(TDI) of aliphatic category polyester polyols (TDI).

At this moment, the Young's modulus of each film of the outer packaging material 13 of the modular ratio of the polyurethane resin of bonding layer 26 formation is all big.In addition, 20 ℃ surface hardness of polyurethane resin is 65, and is bigger than the polyurethane resin shown in the embodiment, and the difference of the surface hardness of 20 ℃ and 0 ℃ is 10.

The Vacuum thermal insulating material that comprises said structure although outer packaging material is peeled off, produces a large amount of pin holes, and breaks.

(Comparative Example D)

Bonding layer 26 is to make of the polyurethane resin that contains aromatic system kind polyester polyatomic alcohol polybasic alcohol and toluene di-isocyanate(TDI) (TDI).

At this moment, the Young's modulus of each film of the outer packaging material 13 of the modular ratio of the polyurethane resin of bonding layer 26 formation is all big.In addition, 20 ℃ surface hardness of polyurethane resin is 68, and is bigger than the polyurethane resin shown in the embodiment, and the difference of the surface hardness of 20 ℃ and 0 ℃ is 12.

Peel off although comprise the outer packaging material of the Vacuum thermal insulating material of said structure, produce a large amount of pin holes, and break.

Herein, the weak peeling strength interface of the laminating body among the present invention is meant, according to the interface a little less than the tensile shear power of the determination of test method of JIS K6850, or according to the interface a little less than the peeling strength of the determination of test method of JIS K6854.

The industry utilizability

As top, vacuum heat insulation materials of the present invention can be grown in the pinhole resistance excellence Phase is kept excellent heat-insulating property.

Therefore, can keep deep freezer, the dwelling house of heat-insulating property in must be between long-term and live Use without problems in the purposes such as residence home appliance. And then, because the gas barrier property excellence, therefore can be effective Ground is as the solar heat protection evil of information equipments such as printing machine, duplicator, liquid crystal projection apparatus, notebook computer etc. The heat-insulating material that countermeasure is used.

In addition, because anti-pin hole excellence, be applicable to the surface etc. of Vacuum thermal insulating material being processed into tortuous or cylindric or compre sion molding Vacuum thermal insulating material, the processability of Vacuum thermal insulating material is had improvement significantly.Therefore, application has been improved, can be easily in out of use local use in the past.

In addition, the Vacuum thermal insulating material of the application of the invention, even can provide at low temperatures use, the reduction of anti-pin hole is very little, even also have the cold insulation equipment of the high-quality of stabilized quality in the equipment that uses below normal temperature.

Claims (21)

1. a Vacuum thermal insulating material is the outer packaging material that contains core at least and coat above-mentioned core, and the inside of above-mentioned outer packaging material is depressurized the Vacuum thermal insulating material that is sealed to form, it is characterized in that,

Above-mentioned outer packaging material is a laminating body, described laminating body contain plastic pellicle more than 2 layers, metal layer and with above-mentioned more than 2 layers plastic pellicle and the above-mentioned bonding bonding layer of metal layer, perhaps described laminating body contain the plastic pellicle more than 2 layers, ceramic evaporation layer and with above-mentioned more than 2 layers plastic pellicle and the above-mentioned bonding bonding layer of ceramic evaporation layer

Above-mentioned laminating body is to possess the laminating body that stress relaxes structure at internal layer, and described stress relaxes the propagation of breaking that structure can prevent to run through the Vertical direction that above-mentioned laminating body acts on like that,

Relax structure as above-mentioned stress, because thrusting of foreign matter makes above-mentioned laminating body be subjected under the situation of compressive stress of Vertical direction, at least contain a kind of structure in following 2 kinds of structures, promptly, the structure that the structure that peel off at a certain interface of above-mentioned laminating body and one of above-mentioned two-layer above plastic pellicle or above-mentioned bonding layer break.

2. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, it is following structure that above-mentioned stress relaxes structure, promptly

On above-mentioned core, place the glass slag, outside decompression is above-mentioned packaging material inside to the condition below the 13Pa,

In the internal layer of above-mentioned laminating body, can block the breaking of the 1st plastic pellicle that causes by thrusting of above-mentioned glass slag and propagate to the 2nd plastic pellicle in the outer layer side adjacency.

3. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, above-mentionedly peels off the interface that the interface is above-mentioned bonding layer and other layer.

4. Vacuum thermal insulating material as claimed in claim 1 is characterized in that above-mentioned metal layer is an evaporated metal layer, and the above-mentioned interface of peeling off is interface between above-mentioned evaporated metal layer and other layer.

5. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, above-mentioned plastic pellicle more than 2 layers contains the coextruded multilayer film, and the above-mentioned interface of peeling off is the interior interface of above-mentioned co-extrusion film.

6. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, it is 100～300N/cm that above-mentioned laminating body contains shear strength ²The interface.

7. Vacuum thermal insulating material as claimed in claim 1 is characterized in that above-mentioned metal layer is an evaporated metal layer, and the interface of above-mentioned evaporated metal layer and other layer is that shear strength is 100～300N/cm ²The interface.

8. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, above-mentioned plastic pellicle more than 2 layers contains the coextruded multilayer film, and the interface in the above-mentioned coextruded multilayer film is that shear strength is 100～300N/cm ²The interface.

9. Vacuum thermal insulating material as claimed in claim 1, above-mentioned bonding layer forms trellis.

10. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, above-mentioned laminating body contains the interface that peeling strength is 20～200N/m.

11. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, above-mentioned plastic pellicle more than 2 layers contains the coextruded multilayer film, and the interface in the above-mentioned coextruded multilayer film is that peeling strength is the interface of 20～200N/m.

12. Vacuum thermal insulating material as claimed in claim 1 is characterized in that, above-mentioned metal layer is an evaporated metal layer, and the interface of above-mentioned evaporated metal layer and other layer is that peeling strength is the interface of 20～200N/m.

13. Vacuum thermal insulating material as claimed in claim 1, any in above-mentioned plastic pellicle or the above-mentioned bonding layer, shear strength are 100～300N/cm ²

14. Vacuum thermal insulating material as claimed in claim 1, the Young's modulus of the above-mentioned plastic pellicle of modular ratio of above-mentioned bonding layer is little.

15. Vacuum thermal insulating material as claimed in claim 13, above-mentioned bonding layer are polyurethane resin.

16. Vacuum thermal insulating material as claimed in claim 15, above-mentioned polyurethane resin contains polyisocyanates and polyester polyol, and with respect to above-mentioned polyester polyol, the equivalent proportion of above-mentioned polyisocyanates is 1～3.

17. Vacuum thermal insulating material as claimed in claim 1, one deck at least of above-mentioned bonding layer is a polyurethane resin, and above-mentioned polyurethane resin contains polyisocyanates and polyester polyol, and with respect to above-mentioned polyester polyol, the equivalent proportion of above-mentioned polyisocyanates is 1～3.

18. Vacuum thermal insulating material as claimed in claim 1, one deck at least of above-mentioned bonding layer is a polyurethane resin, and above-mentioned polyurethane resin comprises the aliphatic category polyisocyanates.

19. Vacuum thermal insulating material as claimed in claim 1, one deck at least of above-mentioned bonding layer is a polyurethane resin, and above-mentioned polyurethane resin contains the pure and mild aliphatic category polyisocyanates of aliphatic category polyester polyols.

20. cold insulation equipment, be the cold insulation equipment that the temperature province below normal temperature is used, in the outer container of described cold insulation equipment and space that interior box-shaped becomes, filled in the body of thermal insulating box of hard resin foam and in the insulated door body at least one, in above-mentioned between case and the above-mentioned outer container and then contain Vacuum thermal insulating material, above-mentioned Vacuum thermal insulating material, it is the outer packaging material that contains core at least and coat above-mentioned core, and the inside of the above-mentioned outer packaging material of reduced pressure sealing and the Vacuum thermal insulating material that forms, it is characterized in that, above-mentioned outer packaging material is a laminating body, described laminating body contains the plastic pellicle more than 2 layers, metal layer and with plastic pellicle more than 2 layers and the bonding bonding layer of metal layer, perhaps, described laminating body contains the plastic pellicle more than 2 layers, pottery evaporation layer and with plastic pellicle more than 2 layers and the bonding bonding layer of ceramic evaporation layer, above-mentioned laminating body, be to possess the laminating body that stress relaxes structure at internal layer, the structure that relaxes described stress can relax above-mentioned laminating body is run through like that and the compressive stress of the Vertical direction of effect

Relax structure as above-mentioned stress, because thrusting of foreign matter makes above-mentioned laminating body be subjected under the situation of compressive stress of Vertical direction, at least contain a kind of structure in following 2 kinds of structures, promptly, the structure that the structure that peel off at a certain interface of above-mentioned laminating body and one of above-mentioned two-layer above plastic pellicle or above-mentioned bonding layer break.

21. cold insulation equipment as claimed in claim 20, above-mentioned Vacuum thermal insulating material contains following outer packaging material, one deck at least of above-mentioned bonding layer be polyurethane resin, above-mentioned polyurethane resin contain polyisocyanates and polyester polyol, with respect to above-mentioned polyester polyol, the equivalent proportion of above-mentioned polyisocyanates is 1～3.

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