CN101178145A - Vacuum insulation material and vacuum flask employing the same - Google Patents
Vacuum insulation material and vacuum flask employing the same Download PDFInfo
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- CN101178145A CN101178145A CNA2007101692438A CN200710169243A CN101178145A CN 101178145 A CN101178145 A CN 101178145A CN A2007101692438 A CNA2007101692438 A CN A2007101692438A CN 200710169243 A CN200710169243 A CN 200710169243A CN 101178145 A CN101178145 A CN 101178145A
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Abstract
The invention provides a vacuum thermal insulation material, which at least consists of lamination membrane decompressing sealing core material provided with polyethylene and vinyl alcohol multipolymer membrane. The single side of the polyethylene and vinyl alcohol multipolymer membrane has vapor deposition membrane and a coating layer which is near the vapor deposition membrane and has inorganic substances in the polyvinyl alcohol; the entire thickness of the coating layer is higher than 16 mum and the outer side has 40 DEG C and 90%RH membrane whose water vapor penetrability is below 0.9g/m2/day.
Description
Technical field
The present invention relates to have long-term reliability, stable on heating vacuum heat insulation material and with this vacuum heat insulation material as the vacuum flask of thermal-protective material.
Background technique
All the time, in the structure of vacuum heat insulation material as the vacuum flask of thermal-protective material, contain water storage with container, heat this water storage with the heater of the interior water of container, to the water route that goes out of outside water outlet.And this vacuum flask has uses the sheath material that is made of stable on heating laminated film to coat the vacuum-packed vacuum heat insulation material of core.This laminated film begins to comprise hot melt coating, gas barrier layer and protective layer from the inboard, the heat seal lands of folding vacuum heat insulation material is with the outside near electric water heater.
As the prior art document relevant, known just like No. 3590720 communique of special permission with the invention of this vacuum flask.
And, for this vacuum flask have curvature portion by deposited parts, the state that is out of shape with core that inorfil coremaking material is constituted, tabular vacuum heat insulation material that thickness is 0.1～6mm is along being fixed by the curvature portion of coating material.
As the prior art document relevant, known just like TOHKEMY 2007-50521 communique with the invention of this vacuum flask.
But in above-mentioned structure in the past, as the stable on heating laminated film of vacuum heat insulation material, polypropylene is used to the hot melt coating of laminated film.Therefore, the core that will be made of the fiber based material of glass fibre etc. when being processed into cylindrical shape, sometimes from inboard pierces through laminated film as the glass fibre of core as core.At this moment, because may produce aperture on the laminated film, so the problem that has is: must carefully note processing conditions and management thereof.
In addition, as the stable on heating laminated film of vacuum heat insulation material, polypropylene is used to the hot melt coating of laminated film.That is, because polyacrylic fusing point is up to about 180 ℃, so when making vacuum heat insulation material, for example with the laminated film bag time, heat-sealing temperature must be elevated to more than the polyacrylic fusing point.If this heat-sealing temperature does not reach more than the polyacrylic fusing point, then heat seal strength is difficult for stablizing, so have following problem: the narrow range of the temperature conditions of bag, the temperature treatment of bag are very difficult.
And, in the past,, also used the gas barrier layer that constitutes by high-density polyethylene resin through the innermost layer of being everlasting as sheath material.For this reason, when the core that will be made of the fiber based material of glass fibre etc. was processed into cylindrical shape as core especially, have following problem: the glass fibre as core pierced through laminated film from the inboard, may produce the hole.
In addition because the fusing point of high-density polyethylene resin up to 132 ℃～135 ℃, so, make vacuum heat insulation material, for example during the bag laminated film, heat-sealing temperature must be brought up to more than the fusing point of high density polyethylene (HDPE).Therefore, if heat-sealing temperature is not brought up to more than the fusing point of high density polyethylene (HDPE), have following problem: the heat-sealable material of low temperature stable insufficient, heat seal strength changes.
On the other hand, the vacuum heat insulation material that is used for this vacuum flask is made as laminated film, and this laminated film obtains poly ethylene vinyl alcohol co-polymer membrane and the polyethylene terephthalate thin film that is provided with vapor-deposited film mutually with its evaporation face applying.
As the prior art document relevant with the invention of this vacuum heat insulation material, known have a fair strictly according to the facts 3-41198 communique.
Fig. 5 is illustrated in the laminated film that forms on the hot melt coating 6 of the vacuum heat insulation material of putting down in writing in the fair 3-41198 communique of reality of prior art document in the past.This laminated film is made of following film: this film be will be provided with vapor-deposited film 5a poly ethylene vinyl alcohol copolymer film 5c and be provided with the polyethylene terephthalate thin film 4 of vapor-deposited film 4a, the film that fits and form with the evaporation face of vapor-deposited film 4a and vapor-deposited film 4b each other.And this laminated film disposes as shown in Figure 5, so that polyethylene terephthalate thin film 4 is positioned at the outside.
And the vacuum heat insulation material that is used for this vacuum flask in the plural layers of lamination, is provided with the enhancement layer 7 that ethylene-vinyl alcohol copolymer and inorganic based material are mixed as shown in Figure 6.
As the prior art document relevant, known just like TOHKEMY 2006-29686 communique with the invention of this vacuum heat insulation material.
Fig. 6 represents the laminated film that forms on the hot melt coating 6 of the vacuum heat insulation material in the past put down in writing in the TOHKEMY 2006-29686 communique of prior art document.The polyethylene terephthalate thin film 4 that is provided with vapor-deposited film 4a with equidirectional 2 layers of arrangement, is formed 2 double-layers.And this laminated film between hot melt coating 6 and above-mentioned 2 double-layers, is provided with the enhancement layer 7 with ethylene-vinyl alcohol copolymer and the mixing of inorganic based material as shown in Figure 6, is provided with nylon resin 3 as skin.
But, because in above-mentioned structure in the past, the gas barrier performance is insufficient, so have following problem: when using in the purposes under the high temperature about 100 ℃, gas is invaded vacuum heat insulation material, cause heat-shielding performance through the time deterioration, the life expectancy of vacuum heat insulation material shortens.
Summary of the invention
The purpose of this invention is to provide a kind of vacuum heat insulation material, this vacuum heat insulation material can solve above-mentioned problem in the past, even when using in the purposes under its high temperature about 100 ℃, also has sufficient heat resistance and long-term reliability.
And, the purpose of this invention is to provide a kind of vacuum flask, this vacuum flask has the vacuum heat insulation material of sufficient heat resistance and long-term reliability by use, improves the heat resistance and the long-term reliability of heat-sealing.
In order to achieve the above object, vacuum heat insulation material of the present invention is to come the reduced pressure sealing core to form with the laminated film that has the poly ethylene vinyl alcohol copolymer film at least, above-mentioned poly ethylene vinyl alcohol copolymer film is at the coating layer that contains organic/inorganic substance in polyvinyl alcohol that has vapor-deposited film and the above-mentioned vapor-deposited film of adjacency on the single face, its integral thickness is more than the 16 μ m, above-mentioned laminated film contains following structure, and its water vapor penetrability that possesses 40 ℃ of 90%RH on the outside of above-mentioned poly ethylene vinyl alcohol copolymer film is 0.9g/m
2The film that/day is following.
By making such structure, the thickness that is used for the poly ethylene vinyl alcohol copolymer film of laminated film is more than the 16 μ m, so can reduce the gas barrier performance that oxygen penetration improves laminated film.And then laminated film is in the outside of poly ethylene vinyl alcohol copolymer film, and the water vapor penetrability that possesses 40 ℃ of 90%RH is 0.9g/m
2The film that/day is following.Thus, can keep moisture-proof, so the gas barrier performance of laminated film is difficult for deterioration.Therefore, can become the vacuum material that possesses laminated film with heat resistance and long-term reliability.
And in order to reach above-mentioned purpose, vacuum flask of the present invention contains following structure, and it possesses shell, be disposed at the bottom tube-like inner container is arranged, being disposed at the vacuum heat insulation material of the above-mentioned record between this inner container and the shell of storage hot water of this shell inboard.
And, applied by hot melt each other between the laminated film of face around the core, can be the part bending that will be between the laminated film be applied by hot melt each other structure in the inner container outside.
And inner container can be to use the structure of the vacuum heat-insulation container that has vacuum layer in wall.
And laminated film can be to have the hot melt coating that is made of low density polyethylene at inner face, towards the structure of being applied by hot melt each other between the core laminated film on every side.
By making such structure, in inner container, use the vacuum heat-insulation container, so compare the temperature step-down in the outside of the inner container when vacuum flask uses during with the inner container that do not use the vacuum heat-insulation container.Thus, even low density polyethylene is used for the sheath material of vacuum heat insulation material, the temperature of the sheath material when vacuum flask uses the also temperature than the low density polyethylene fusion is low.Therefore, by using low density polyethylene, come to compare with the situation of using polypropylene or high density polyethylene (HDPE), mechanical strengths such as the anti-permeability of laminated film, heat seal strength, tensile yield strength can further improve.Therefore, the quality of vacuum heat insulation material be can improve, and the producibility and the reliability of vacuum flask improved.
Description of drawings
Fig. 1: the sectional view of the vacuum heat insulation material of expression embodiment of the present invention 1.
Fig. 2: the enlarged cross section figure of the laminated film of the vacuum heat insulation material of expression embodiment of the present invention 1.
Fig. 3: the summary sectional view of the vacuum flask of embodiment of the present invention 2.
Fig. 4: the oblique drawing of employed vacuum heat insulation material in embodiment of the present invention 2.
Fig. 5: the sectional view of the laminated film of expression vacuum heat insulation material in the past.
Fig. 6: the sectional view of the laminated film of expression vacuum heat insulation material in the past.
Symbol description
1: core
2: laminated film
3: resin layer
4: polyethylene terephthalate thin film
4a: vapor-deposited film
5: layer laminate
5a: vapor-deposited film
5b: coating layer
5c: poly ethylene vinyl alcohol copolymer film
6: the hot melt coating
7: enhancement layer
10: vacuum flask
11: shell
12: inner container
12a: top opening portion
13: vacuum heat insulation material
Embodiment
Below, embodiments of the present invention are described with accompanying drawing.In following accompanying drawing, for the ease of understanding structure each size amplified and to represent.And, for similar elements,, omit explanation sometimes owing to used same-sign.
Mode of execution 1
Fig. 1 is the sectional view of the vacuum heat insulation material of embodiment of the present invention 1.Fig. 2 is the amplification sectional view of laminated film of the vacuum heat insulation material of identical mode of execution 1.
As shown in Figure 1, vacuum heat insulation material is made of the core 1 and the laminated film 2 of porous matter, after among the laminated film 2 of core 1 insertion system pouch, carries out vacuum exhaust, internal pressure is about below the 200Pa, around the core 1 towards laminated film 2 between applied by hot melt each other.
In core 1, can use inorganic powders such as inorfils such as glass fibre, rock wool and silica etc., preferably use under the high temperature about 100 ℃ shape invarianceization and do not produce the material of gas.
And, sorbent can be packed in the laminated film 2 with core 1.As sorbent, be the adsorbability material of adsorbent and moisture adsorbent etc., so long as have degree of vacuum effect that reduces vacuum heat insulation material or the material of keeping the degree of vacuum effect, just be not particularly limited.
As shown in Figure 2, laminated film 2 has resin layer 3, polyethylene terephthalate thin film 4, vapor-deposited film 4a, coating layer 5b, vapor-deposited film 5a, poly ethylene vinyl alcohol copolymer film 5c, hot melt coating 6 from the outside to the inboard.
In poly ethylene vinyl alcohol copolymer film 5c, on its single face, form vapor-deposited film 5a, abutted to form the coating layer 5b that in polyvinyl alcohol, contains organic/inorganic substance with this vapor-deposited film 5a, as a whole, comprised that poly ethylene vinyl alcohol copolymer film 5c has constituted 3 layers layer laminate 5.The integral thickness of this layer laminate 5 is more than the 16 μ m.
And laminated film 2 possesses the polyethylene terephthalate thin film 4 that has vapor-deposited film 4a on single face on the outside of poly ethylene vinyl alcohol copolymer film 5c.The polyethylene terephthalate thin film 4 that has vapor-deposited film 4a on single face is that the water vapor penetrability of 40 ℃ of 90%RH is 0.9g/m
2The film that/day is following.As shown in Figure 2, the vapor-deposited film 4a with polyethylene terephthalate thin film 4 adjacency is that face contacts with coating layer 5b.
For the vacuum heat insulation material of the present embodiment that constitutes in the above-described manner, below its effect of explanation.
At first, in constituting the laminated film 2 of vacuum heat insulation material, the relation table of the oxygen penetration of the integral thickness of layer laminate shown in Figure 25 and 100 ℃ of 0%RH is shown in Table 1.In table 1, the integral thickness of layer laminate 5 is expressed as covering material+VM-EVOH thickness.VM-EVOH is meant the polyethylene terephthalate thin film 4 with vapor-deposited film 4a.
Here; the laminate film 2 that is used to estimate comprises following structure; from outermost surface; its have as the thickness of resin layer 3 of protection usefulness be 25 μ m nylon film (below; be called " Ny "); contain thickness and be the vapor-deposited film 4a of 12 μ m polyethylene terephthalate thin film (below; be called " PET-VM ") 4; the coating layer 5b that in thickness is the polyvinyl alcohol of 1 μ m, contains organic/inorganic substance; contain vapor-deposited film 5a the poly ethylene vinyl alcohol copolymer film (below; be called " VM-EVOH ") 5c; as the thickness of hot melt coating 6 is the no extended polypropylene film (below, be called " CPP ") of 50 μ m.Here, the thickness of VM-EVOH is made into 11 μ m, 13 μ m, 15 μ m, 17 μ m.
In the present embodiment, use this film of Ny (nylon film), use this film of CPP (no extended polypropylene film) as hot melt coating 6 as resin layer 3.But the film of resin layer 3 and hot melt coating 6 is not limited to above-mentioned material, can be made of film combinations such as metal foils such as aluminium, the film with metal beyond the aluminium or oxide-free vapor-deposited film, this polyethylene of straight-chain low density polyethylene.
The oxygen penetration of 100 ℃ of 0%RH is with JIS K7126B method (equal-pressure method), with on average measuring of sample several 2.
From the result shown in the table 1, as can be seen covering material+VM-EVOH thickness is made more than the 16 μ m, can make oxygen penetration at the 1.0ml/m that measures threshold value
2Below/the day/MPa.
Table 1
| Covering material+VM-EVOH thickness μ m | Oxygen penetration ml/m
2/day/ |
| 12 | 3.9 |
| 14 | 2.0 |
| 16 | 1.0 below |
| 18 | 1.0 below |
This is based on following effect.
VM-EVOH5c comes crystallization by extending orientation on manufacturing process, particularly little by little two extensions, and the solid structure at fibrillating on the bearing of trend can be stretched on width direction in advance.Thus, on VM-EVOH5c, produce defective, have and cause the not characteristic of gentle punching of stretching.
In other words,, there is the limit aspect the suitable thickness,,, can not causing the not gentle punching of stretching, because the thickness of VM-EVOH5c is suitably changed by increasing thickness so do the time spent at the compression pressure that as vacuum heat insulation material, is subjected to atmosphere by processing.
Simultaneously, on single face, have among the VM-EVOH5c of vapor-deposited film 5a,, also have the effect that reduces oxygen penetration, improves the gas barrier performance by further on vapor-deposited film 5a, being arranged on the coating layer 5b that contains organic/inorganic substance in the polyvinyl alcohol.
By in the high polyvinyl alcohol of oxygen breathability, containing organic/inorganic substance, make mineral filler be dispersed in the polyvinyl alcohol.And mineral filler is stacked densely, and when making oxygen or water vapor by coating layer, the effect of balk board is played in the mineral filler meeting, so the gas permeation path of can extending significantly.In other words, the thickness that the effect of playing just likes the polyvinyl alcohol layer that the gas barrier performance is high increases tens of times.
Further, by being arranged on the coating layer 5b that contains organic/inorganic substance in the polyvinyl alcohol on vapor-deposited film 5a, and the effect that has is: improve the evaporation effect,, gas barrier performance good with the adaptation of aluminium-vapour deposition film uprises.
In table 1, the value of oxygen penetration is 1.0ml/m
2Below/the day/MPa.Owing to can't measure than its low value, so adopt this kind mark here.On the VM-EVOH5c with vapor-deposited film 5a, further when the thickness of the film that is arranged on the coating layer 5b that contains organic/inorganic substance in the polyvinyl alcohol on vapor-deposited film 5a was 16 μ m to 18 μ m, can infer in fact also was the low film of oxygen penetration.
Therefore, VM-EVOH5c have on the single face vapor-deposited film 5a, with the coating layer 5b that in polyvinyl alcohol, contains organic/inorganic substance of this vapor-deposited film 5a adjacency, constitute poly ethylene vinyl alcohol copolymer layer 5 as a whole.By the integral thickness that makes this poly ethylene vinyl alcohol copolymer layer 5 is more than the 16 μ m, and the value that can make oxygen penetration is 1.0ml/m
2Below/the day/MPa, realize the low film of oxygen penetration.
By more than, when using in the purposes under the high temperature of vacuum heat insulation material about 100 ℃, because gas barrier performance height, can not be subjected to the influence of outside oxygen etc., so the extremely difficult deterioration by the time that causes the heat-shielding performance of vacuum heat insulation material.Therefore, vacuum heat insulation material of the present invention can obtain the life expectancy of sufficient thermal-protective material, can realize high reliability.
In addition, on VM-EVOH5c, and then on vapor-deposited film 5a, have the coating layer 5b that in polyvinyl alcohol, contains organic/inorganic substance, owing to use film to be used for vacuum heat insulation material, be the material of possess hydrophilic property so should expect poly ethylene vinyl alcohol copolymer and polyvinyl alcohol with this spline structure.
That is, in the film of the moisture absorption that contains the poly ethylene vinyl alcohol copolymer, can relax the intermolecular combination of the material that constitutes film.Perhaps, in the film of the moisture absorption that contains polyvinyl alcohol copolymer, can relax the hydrogen combination of the material that constitutes film.Thus, because the noncrystalline demi-inflation in the film, penetrability increases, the problem of film characteristics deterioration so can produce oxygen.
Therefore, in the present embodiment,, and be conceived to the film characteristics relevant with the water vapor penetrability as the deterioration strategy that prevents the film characteristics relevant with oxygen penetration.In order to improve the film characteristics relevant with this water vapor penetrability, as shown in Figure 2, produce on the VM-EVOH5c with vapor-deposited film 5a, further fitting in the film outside with coating layer 5b has polyethylene terephthalate thin film 4 materials of vapor-deposited film 4a.
Table 2 is illustrated in the laminated film 2 by the structure that constitutes with Fig. 2 identical materials and thickness, has the relation of the oxygen penetration of the water vapor penetrability of water vapor penetrability, laminated film 2 of 40 ℃ of 90%RH of PET-VM4 of vapor-deposited film 4a and 100 ℃ of 0%RH.
Here, the water vapor penetrability of 40 ℃ of 90%RH shown in the table 2, expression will be made 90%RH as the Ny side of PET-VM4 and resin layer 3 with JIS Z0208 (cup envelope method), measure the result of the mean value of sample 4.
From the result shown in the table 2 as can be seen, the water vapor penetrability with PET-VM4 of vapor-deposited film 4a is 0.9g/m
2When/day was following, the water vapor penetrability of laminated film 2 and oxygen penetration became very low.That is, the water vapor penetrability is at 0.3g/m
2Below/the day, and oxygen penetration is at 1.0ml/m
2Below/the day/MPa, improved the characteristic of film.
Table 2
| PET-VM water vapor penetrability g/m 2/day | Laminated film water vapor penetrability g/m 2/day | Laminated film oxygen penetration ml/m 2/day/MPa |
| 0.5 | 0.2 | 1.0 below |
| 0.8 | 0.3 | 1.0 below |
| 0.9 | 0.3 | 1.0 below |
| 1.0 | 0.6 | 1.5 |
| 1.2 | 0.9 | 2.3 |
| 1.8 | 1.5 | 3.6 |
This is based on following effect.
Water vapor penetrability with PET-VM4 of vapor-deposited film 4a is made up of film density, thickness and film and is decided, and the water vapor penetrability is 0.9g/m
2About/day, can be estimated as the condition that the suitableeest film density, thickness and film are formed.Therefore, poly ethylene vinyl alcohol copolymer and polyvinyl alcohol are difficult to hygroscopic moisture steam, are difficult to cause noncrystalline demi-inflation in the film etc., so the water vapor penetrability of laminated film 2 also becomes extremely low.
The result who brings thus is, the deterioration of the film characteristics that the oxygen penetration that accompanies with the moisture absorption of poly ethylene vinyl alcohol copolymer and polyvinyl alcohol is related also is difficult to produce.
And then, in the present embodiment, make the face of the vapor-deposited film 4a of the PET-VM4 with vapor-deposited film 4a, contact with the coating layer 5b face that coating layer 5b is arranged on the film on the VM-EVOH5c with vapor-deposited film 5a, finish lamination.
Therefore, the hole that vapor-deposited film 4a, 5a are had is configured the material institute landfill of coating layer 5b, is bonded with each other between the face of vapor-deposited film 4a, 5a.Thus, the hole that then can polishing vapor-deposited film 4a, 5a be had so uprise as the vapor-deposited film density of laminated film 2, produces the effect that reduces oxygen penetration and water vapor penetrability, improves film characteristics.
In the present embodiment, to contain thickness be that above poly ethylene vinyl alcohol copolymer layer 5 of 16 μ m and the water vapor penetrability that has 40 ℃ of 90%RH on this layer outside are 0.9g/m to laminated film 2
2The PET-VM4 of the vapor-deposited film 4a that/day is following.
As above, in the present embodiment, poly ethylene vinyl alcohol copolymer layer 5, just on the VM-EVOH5c, the layer that has vapor-deposited film 5a and form at single face with the coating layer 5b of this vapor-deposited film 5a adjacency, by the thickness that makes monolithic film membrane is more than the 16 μ m, can reduce oxygen penetration, so can improve film characteristics.
And then laminated film 2 is to possess the PET-VM4 that contains vapor-deposited film 4a on single face on the outside of poly ethylene vinyl alcohol copolymer layer 5, and this vapor-deposited film 4a is that the water vapor penetrability as 40 ℃ of 90%RH is 0.9g/m
2The film that/day is following.The vapor-deposited film 4a of this PET-VM4 is that face contacts with the coating layer 5b of poly ethylene vinyl alcohol copolymer layer 5.Thus, by keep the film moisture-proof relevant with kilter, can improve the gas barrier performance of 2 pairs of oxygen of laminated film etc. with the water vapor penetrability.
So the vacuum heat insulation material of present embodiment even use in the purposes under the high temperature about 100 ℃, does not have yet and is subjected to outside oxygen influence etc., thus the extremely difficult heat-shielding performance that causes vacuum heat insulation material through the time deterioration.Therefore, vacuum heat insulation material of the present invention can obtain the heat-resisting time limit of sufficient thermal-protective material, can realize high reliability.
Mode of execution 2
Fig. 3 is the summary sectional view of the vacuum flask 10 of embodiments of the present invention 2.In this vacuum flask 10, use be in the mode of execution 1 explanation vacuum heat insulation material of the present invention.
As shown in Figure 3, the vacuum flask 10 of present embodiment possess shell 11, be disposed at the storage hot water of shell 11 inboards the inner container that bottom tube-like is arranged 12, covering shell 11 at least a portion top and inner container 12 top opening portion 12a lid 13, be disposed at the vacuum heat insulation material 14 between inner container 12 and the shell 11.The material of explanation is identical in this vacuum heat insulation material 14 and the mode of execution 1, is to come the reduced pressure sealing core at the sheath material that inner face has a hot melt coating, is applied by hot melt each other between the sheath material around the core, thereby produces vacuum heat insulation material.And, in the vacuum flask 10,, for example using the vacuum heat-insulation container that in wall, has vacuum layer as inner container 12, the material as the hot melt coating of vacuum heat insulation material 14 for example uses low density polyethylene.
Here, the vacuum heat-insulation container is to occupy internal layer and outer field dual structure are arranged, and is provided with the space of vacuum decompression within it between layer and the skin, and it is called as " magic bottle ".Material mainly uses stainless steel.
Fig. 4 is 14 a oblique drawing of employed vacuum heat insulation material in the vacuum flask 10 of embodiment of the present invention.
As shown in Figure 4, in the vacuum flask 10 of embodiment of the present invention 14 of employed vacuum heat insulation material,, and be processed into flat vacuum heat insulation material 14 cylindric for the outer circumferential face along overlay content device 12 curls.The part of joint is to wait by band with Adhesion force or binder to connect.There is no particular restriction for the material of band and binder, so long as can connect with the material of keeping cylindrical shape just passable.
In the present embodiment, the part towards being applied by hot melt each other between the core sheath material on every side of vacuum heat insulation material 14 is bent the outside at inner container 12.Thus, the part of being applied by hot melt of sheath material is folded to the outside of inner container, makes the temperature step-down of the part that the hot melt of sheath material applies.
In fact, the vacuum flask 10 of present embodiment is that 3L, initial stage water temperature are that 20 ℃, insulation water temperature are that 90 ℃, atmosphere temperature are under 20 ℃ the condition in the water yield, and when measuring sheath material and being applied the temperature of part by hot melt, circumference temperature everywhere all is below 65 ℃.
And vacuum heat insulation material 14 is the materials that are made of core, sheath material at least.Core can be the such inorfil system of glass fibre, rock wool, the powder system that organic fiber is, silica is such that polyester fibre is such etc., and there is no particular restriction.
Sheath material is the laminated film that is made of a plurality of films.In the present embodiment, on the hot melt coating of sheath material, use the material adopt low density polyethylene for example and to make.
Here, the structure of laminated film that is used for described temperature measuring is identical on the two sides, all is to be that the nylon film of 25 μ m, nylon film, the thickness that thickness is 15 μ m are that 6 μ m aluminium foils, thickness are the straight chain shape low-density polyethylene film of 50 μ m from the thickness that outermost surface begins.
And the continuous heat resisting temperature boundary of straight chain shape low density polyethylene is 95 ℃ to 100 ℃, is that 130 ℃, the continuous heat resisting temperature boundary of high density polyethylene (HDPE) are 110 ℃ and compare with polyacrylic continuous heat-resisting boundary, has the low characteristic of continuous heat resisting temperature boundary.
Table 3 is figure of properties of materials difference used in the hot melt coating of laminated film of expression sheath material.That is, represent that relatively low density polyethylene (hereinafter referred to as " LDPE "), straight chain shape low density polyethylene (hereinafter referred to as " LLDPE "), metalloscene catalyst are the property difference of straight chain shape low density polyethylene (hereinafter referred to as " mLLDPE "), high density polyethylene (HDPE) (hereinafter referred to as " HDPE "), polypropylene (hereinafter referred to as " CPP ").
As can be seen from Table 3, the difference of LDPE and HDPE can be decided by density.That is, if compare 940kg/m
3High density is exactly HDPE, if compare 940kg/m
3Low density is exactly various LDPE.
But in the time can not judging LDPE and HDPE with density, the fusing point shown in the table 3 is made judgement by inquiry.
And LDPE compares with polypropylene or HDPE, has the strong characteristic of mechanical strength such as anti-permeability, heat seal strength, tensile yield strength of laminated film.
Table 3
| Project | LDPE | LLDPE | mLLDPE | HDPE | CPP |
| Density Kg/m 3 | 910～925 | 915～945 | 900～940 | 941～965 | 900 |
| Fusing point ℃ | 105～110 | 122～127 | 95～128 | 132～135 | 176 |
| Continuous heat resisting temperature boundary ℃ | 85 | 95～100 | 75～100 | 110 | 130 |
As previously mentioned, the part of being applied by hot melt each other between the sheath material around the core with vacuum heat insulation material 14, bending is in the outside of inner container 12, and sheath material is below 60 ℃ by the temperature of the part that hot melt applies.Thus, even the LDPE that fusing point is lower is used for the material of vacuum heat insulation material 14 of the vacuum flask 10 of present embodiment, the strong characteristic of the above-mentioned described mechanical strength of also sustainable performance, and keep continuous heat resistance.
And, in the present embodiment, use the LLDPE film, but also can use the co-extrusion film of the different materials more than 2 kinds of common ldpe film, mLLDPE film and common ldpe film and this material of LLDPE or same material being extruded and making.
By this way,, also can be the temperature that more can not fuse even in the sheath material of vacuum heat insulation material 14, use LDPE.And, compare with CPP or HDPE, by using LDPE, can further improve the mechanical strengths such as anti-permeability, heat seal strength, tensile yield strength of laminated film.
And, other laminar structure and without particular limitation, for example, can use have nylon, the film of metal or oxide-free vapor-deposited film constitutes beyond polyethylene terephthalate, this metal foil of aluminium foil or the aluminium.
Here, there is no particular restriction to have the film of vapor-deposited film, but following film can be arranged: for example, VM-EVOH is further implemented the film of evaporation, PET-VM is further implemented the film of evaporation, perhaps, each vapor-deposited film surface is further implemented the film of covering material.
And, in the present embodiment, evaporated film is used for the gas barrier layer of the sheath material between core and inner container 12.
In the vacuum flask 10 of present embodiment 2, in actual amount of water is 3L, 20 ℃ of initial stage water temperatures, 90 ℃ of insulation water temperatures, be divided under the condition of 20 ℃ of temperature, measure sheath material applied the temperature of part by hot melt the time, use the mode that evaporated film is used for the film on the gas barrier layer of the sheath material between core and the inner container 12, circumference temperature everywhere all is below 60 ℃.
Here, the structure of employed laminated film when measuring temperature, inner container 12 sides from outermost surface begin be thickness be 25 μ m nylon film, to have PET-VM that thickness is the vapor-deposited film of 12 μ m, have VM-EVOH, the thickness that thickness is the vapor-deposited film of 12 μ m be the ldpe film of 50 μ m.
And it is that the nylon film of 25 μ m, the nylon film that thickness is 15 μ m, aluminium foil, the thickness that thickness is 6 μ m are the ldpe film of 50 μ m that shell 11 sides begin from outermost surface.
Specifically compared with previous described temperature measuring, temperature is low about 5 ℃, this is because will apply the gas barrier layer that the film of vapor-deposited film is used for the sheath material between core and inner container 12, tail off the temperature step-down of the part of being applied of sheath material by hot melt so come from the heat leak of inner container 12.
Thus, even in the sheath material of vacuum heat insulation material 14, use LDPE as can be seen, also can become and more can keep continuous stable on heating temperature.
Therefore, compare, LDPE can be used for the sheath material of vacuum heat insulation material 14, can further improve the mechanical strength such as anti-permeability, heat sealability, tensile yield strength of laminated film with CPP or HDPE.
And then mechanical strengths such as the anti-permeability by improving laminated film, heat sealability, tensile yield strength can reduce glass fibre and pierce through laminated film from the inboard, produce the possibility in hole.
And, by use LDPE, the heat-sealing temperature in the time of can reducing the bag laminated film, thus can improve the heat-sealing stability of low temperature, and make heat seal strength stable.
As mentioned above, the vacuum flask 10 of present embodiment possess shell 11, be disposed at the storage hot water of shell 11 inboards the inner container that bottom tube-like is arranged 12, covering shell 11 at least a portion top and inner container 12 top opening portion 12a lid 13, be disposed at the vacuum heat insulation material 14 between inner container 12 and the shell 11.This vacuum heat insulation material 14 is identical with the material of explanation in the mode of execution 1, is to come the reduced pressure sealing core by the sheath material that has the hot melt coating at inner face, is applied by hot melt each other between core sheath material on every side, thereby produces vacuum heat insulation material.And, in the vacuum flask 14,, for example using the vacuum heat-insulation container that in wall, has vacuum layer as inner container 12, the material as the hot melt coating of vacuum heat insulation material 14 for example uses low density polyethylene.And the part towards being applied by hot melt each other between the core sheath material on every side of vacuum heat insulation material 14 is bent in the outside of inner container 12, and, on the gas barrier layer of the sheath material between core and the inner container 12, using evaporated film.
And, in the present embodiment, the vacuum heat-insulation container is used for inner container 12, so compared with the inner container 12 that does not use the vacuum heat-insulation container, the temperature step-down in the outside of the inner container 12 when vacuum flask 10 uses.Therefore, even LDPE is used for the sheath material of vacuum heat insulation material 14, the temperature of the sheath material when vacuum flask 10 uses is lower than the temperature of LDPE fusion.Thus, the good LDPE of characteristic such as mechanical strength can be used,, the mechanical strength such as anti-permeability, heat seal strength, tensile yield strength of laminated film can be further improved so compare with the situation that CPP or HDPE is used for laminated film.
And, by the part bending of will be applied by hot melt each other between the sheath material around the core of vacuum heat insulation material 14 the outside at inner container 12, do not bend when using in the situation in the outside of inner container 12 and compare, the temperature step-down of the part of being applied by hot melt each other between the exterior material with vacuum flask 10.Therefore, the temperature of the part of being applied by hot melt each other between the exterior material is lower than the temperature of LDPE fusion.
And by evaporated film being used for the gas barrier layer of the sheath material between core and inner container 12, the heat leak that comes from inner container 12 tails off, so the temperature step-down of the part that sheath material is applied by hot melt.
Therefore,, can further improve the quality of vacuum heat insulation material 14, further improve the producibility of vacuum flask 10 by the above.
Embodiment and comparative example
When making vacuum heat insulation material 14, core is a glass fibre, and the size of the core when vacuum heat insulation material 14 is finished is made the size of 200mm * 650mm * 8mm.
The laminated film of sheath material adds the outside in man-hour at cylinder, and from outermost surface, its structure is the nylon film of thickness 25 μ m, the nylon film of thickness 15 μ m, the aluminium foil of thickness 6 μ m, the hot melt coating film of thickness 50 μ m.
And, the laminated film of sheath material, add the inboard in man-hour at cylinder, from outermost surface, its structure be 25 μ m nylon film, to have PET-VM that thickness is the vapor-deposited film of 12 μ m, have VM-EVOH, the thickness that thickness is the vapor-deposited film of 12 μ m be the hot melt coating film of 50 μ m.
The structure of above vacuum heat insulation material 14, application of vacuum to the degree of vacuum of the vacuum chamber of vacuum package machine is 0.01Torr, produces flat vacuum heat insulation material 14.
Hole count after the cylinder processing
As shown in Figure 4, with flat vacuum heat insulation material 14 be processed into cylindric after, break the sheath material of vacuum heat insulation material 14, measure the hole count on the two sides in inboard and the outside.Hole count is to use hole detector (the hole discovery device TRC-220A that the Sanko electronics is made), measures the measured load of the tale on two sides.Here, the N number of working sample is 10, gets the measured load of their mean value as embodiment.
But, in the hole count of measuring, be also contained on the measuring principle of hole detector the doubtful hole of complete non-through laminated film.
The management temperature range
Investigation can be set as follows the management temperature range of temperature, and promptly heat seal strength is more than the 25N, and applies the heat-sealing temperature that does not produce sintering and cavitation corrosion on the part at hot melt.Heat-sealing temperature is set, be with the central value of the fusing point of each material up and down 5 ℃ be yardstick, the change condition is measured.
Heat seal strength is to measure with the portable testing machine EZTest that Shimadzu Seisakusho Ltd. makes.Here, the N number of the mensuration of the heat seal strength that each temperature is set is 10, and the condition of setting is: the total above heat seal strength of 25N that is is arranged, and do not produce sintering and cavitation corrosion on the deposited part of hot melt.And it is to be taken to the temperature range that is set to the difference of minimum temperature setting from maximum temperature that heat-sealing temperature is set possible management temperature range.
Heat seal strength changes
After becoming the heat-sealing of 10mm wide the laminated film bag, measuring hot melt, to apply length be the heat seal strength of 15mm.Heat seal strength is that the portable testing machine EZTest that adopts Shimadzu Seisakusho Ltd. to make measures.Here, the N number of mensuration is 10, gets the maximum value of its heat seal strength and the difference of minimum value and is used as the heat seal strength variation.
With the results are shown in the table 4 of above condition.In table 4, the comparative example of having represented in the sheath material of the vacuum heat insulation material 14 of above-mentioned explanation, to use the embodiment of LDPE separately and having used CPP and HDPE.And, for the various mensuration shown in above-mentioned, also, obtain relating to the measured load that hole count, management temperature range and heat seal strength after the cylinder shown in the table 4 is processed change on the sheath material of vacuum heat insulation material 14, using the embodiment of LLDPE and mLLDPE to carry out.
Table 4
| Embodiment | Comparative example | ||||
| 1 | 2 | 3 | 1 | 2 | |
| The hot melt coating | LDPE | LLDPE | mLLDPE | HDPE | CPP |
| Hole number after the cylinder processing | 3.6 | 2.1 | 3.0 | 10.5 | 8.3 |
| Management |
5 | 5 | 5 | 10 | 15 |
| Heat seal strength changes N | 3.9 | 3.5 | 2.6 | 15.4 | 10.9 |
As can be seen from Table 4, in the sheath material of vacuum heat insulation material, use among the embodiment of LDPE, LLDPE and mLLDPE, compare with the use HDPE of comparative example and the situation of CPP, the hole count that demonstrates after cylinder is processed is 2.1 to 3.0, i.e. low value below 1/2.Equally, change, demonstrate and be 2.6N to 3.9N in an embodiment, be the value of the variation below 1/2 of 10.9N to 1 5.4N of comparative example for heat seal strength.
This shows, in the vacuum heat insulation material 14 in the mechanical strengths such as the anti-permeability of used laminated film, heat seal strength, tensile yield strength, use embodiment's LDPE, LLDPE and among the mLLDPE each, compare with each of HDPE that uses comparative example and CPP, intensity is very strong, and intensity stabilization.
On the other hand, compare for 10 ℃ to 15 ℃ of the management temperature range in the table 4 and comparative example, embodiment is 5 ℃, and scope diminishes, the temperature range of this temperature range for can fully controlling.
When using in the purposes under the vacuum heat insulation material of the present invention, the particularly high temperature about 100 ℃, extremely difficult cause heat-shielding performance through the time deterioration, so can obtain the life expectancy of sufficient thermal-protective material.Therefore, supply with water-heating machine with water tank, warm water use in toilet water tank, vending machine with case, fuel cell with case, automobile with insulations such as case, food with bag, in the insulation of warm plastic bottle or jar all purposes that need thermal insulation such with server, the vacuum flask of container, coffee ﹠ tea with the insulation of the rotating cylinder of container, washing machine, can use, be material of great use.
And, use the vacuum flask of the present invention of above-mentioned vacuum heat insulation material, can further improve the quality of vacuum heat insulation material, improve the producibility of vacuum flask, can be applied to cool-bag that has between shell and inner container in thermal-protective material etc., be material of great use.
Claims (8)
1. a vacuum heat insulation material is characterized in that, it is formed by the laminated film reduced pressure sealing core that has the poly ethylene vinyl alcohol copolymer film at least; Described poly ethylene vinyl alcohol copolymer film is at the coating layer that contains organic/inorganic substance in polyvinyl alcohol that has vapor-deposited film and the described vapor-deposited film of adjacency on the single face, and integral thickness is more than the 16 μ m; Described laminated film possesses 40 ℃ of 90%RH in the outside of described poly ethylene vinyl alcohol copolymer film water vapor penetrability is 0.9g/m
2The film that/day is following.
2. vacuum heat insulation material according to claim 1, wherein, the water vapor penetrability of described 40 ℃ of 90%RH is 0.9g/m
2The following film of/day is to have the polyethylene terephthalate thin film of vapor-deposited film on single face.
3. vacuum heat insulation material according to claim 2, wherein, the vapor-deposited film of described polyethylene terephthalate thin film is that face contacts with described coating layer.
4. a vacuum flask is characterized in that, it possesses shell, be disposed at the bottom tube-like inner container is arranged, being disposed at each the described vacuum heat insulation material of the claim 1 to 3 between described inner container and the described shell of storage hot water of the inboard of described shell.
5. vacuum flask according to claim 4 wherein, is applied by hot melt between the described laminated film around the described core each other, with the part bending of being applied by hot melt each other between the described laminated film outside at inner container.
6. vacuum flask according to claim 4, wherein, the vacuum heat-insulation container that has vacuum layer in the wall with described inner container uses as described inner container.
7. vacuum flask according to claim 6, wherein, described laminated film has the hot melt coating that is made of low density polyethylene at inner face, is applied by hot melt each other between described core described laminated film on every side.
8. vacuum flask according to claim 7, wherein, will be towards the outside of the part bending of being applied by hot melt each other between the described laminated film around the described core at inner container.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006301176 | 2006-11-07 | ||
| JP2006301176A JP2008114520A (en) | 2006-11-07 | 2006-11-07 | Vacuum heat insulation material |
| JP2007144803 | 2007-05-31 |
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| JP5106319B2 (en) * | 2008-08-28 | 2012-12-26 | 日立アプライアンス株式会社 | Vacuum insulation |
| JP6094088B2 (en) * | 2012-08-08 | 2017-03-15 | 大日本印刷株式会社 | Laminate for vacuum insulation |
| KR102172164B1 (en) * | 2012-09-19 | 2020-10-30 | 어플라이드 머티어리얼스, 인코포레이티드 | Methods for bonding substrates |
| JP2014081070A (en) * | 2012-09-28 | 2014-05-08 | Nippon Synthetic Chem Ind Co Ltd:The | Outer bag for vacuum insulation structure and vacuum insulation structure |
| JP2014126098A (en) * | 2012-12-26 | 2014-07-07 | Nippon Synthetic Chem Ind Co Ltd:The | Vacuum insulation structure and outer package bag for vacuum insulation structure |
| JP6450183B2 (en) * | 2014-12-19 | 2019-01-09 | 株式会社クラレ | Vacuum heat insulating material and manufacturing method thereof |
| KR20220054339A (en) | 2019-08-23 | 2022-05-02 | 주식회사 쿠라레 | Multilayer structures, vacuum packaging bags and vacuum insulation |
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