CN102388252B - Vacuum insulation material and device provided with same - Google Patents

Vacuum insulation material and device provided with same Download PDF

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Publication number
CN102388252B
CN102388252B CN201080015047.5A CN201080015047A CN102388252B CN 102388252 B CN102388252 B CN 102388252B CN 201080015047 A CN201080015047 A CN 201080015047A CN 102388252 B CN102388252 B CN 102388252B
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China
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heat insulation
vacuum heat
outsourcing
insulation material
thermofussion welding
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CN102388252A (en
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内田武
大堀进一
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Sharp Corp
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Sharp Corp
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00General constructional features
    • F25D23/06Walls
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25DREFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00Insulation
    • F25D2201/10Insulation with respect to heat
    • F25D2201/14Insulation with respect to heat using subatmospheric pressure

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Insulation (AREA)

Abstract

A vacuum insulation material of excellent heat insulation properties which can overcome the limitation of improvement in conventional heat insulation properties, and a device provided with the vacuum insulation material. The vacuum insulation material (1) is provided with envelope materials (200), a core material (100) contained inside the envelope materials (200), and an adsorbing material (400) contained inside the envelope materials (200). The envelope materials (200) comprise heat-welded portions (300) wherein the envelope materials (200) are heat-welded in contact with each other. The heat-welded portions (300) are formed of a material containing hydrocarbon. The adsorbing material (400) adsorbs hydrocarbon gas.

Description

Vacuum heat insulation material and the equipment with this vacuum heat insulation material
Technical field
The present invention relates to vacuum heat insulation material and the equipment with this vacuum heat insulation material.
Background technique
In the past, in the refrigerator used for heating various food, cooling, be incubated, cooler bin, HEATING BOX etc. and to dried object blowout hot blast to make, in the dryer of dried object drying etc., to use the thermal-protective material with various stuctures and properties.Due among thermal-protective material, the heat-shielding performance of vacuum heat insulation material is excellent, so vacuum heat insulation material is widely used in the equipment such as the heat insulation household refrigerator of needs.Behind the general inside by the core material be made up of inorganic material being filled into outsourcing material, outsourcing material being sealed, and makes the inside of outsourcing material remain in decompression state, thus can vacuum heat insulation material be obtained.
In vacuum heat insulation material, from the core material being filled into outsourcing material inside, produce the inside that water vapour or gas permeation outsourcing material enter into outsourcing material sometimes.If because above-mentioned water vapour or gas make voltage rise in outsourcing material high, then decompression state is made to be deteriorated and heat-shielding performance is reduced.Therefore, in vacuum heat insulation material in the past, in order to prevent voltage rise in outsourcing material high, in outsourcing material inside, there is moisture adsorbent etc.
The vacuum heat insulation material that such as No. 2002-161994, Japanese Laid-Open Patent Publication (patent documentation 1) is recorded utilizes outsourcing material response type moisture adsorbent is encased together with core material and seals.Even if after prepared by vacuum heat insulation material, when the moisture because discharging from core material making voltage rise height in vacuum heat insulation material, response type moisture adsorbent also can be utilized to adsorb and remove moisture, prevent heat-shielding performance to be deteriorated.In this vacuum heat insulation material, response type moisture adsorbent uses: the metallic oxides such as calcium chloride, calcium oxide, lithium chloride, magnesium oxide; Or the physical absorbent such as silica gel, zeolite.
In addition, the vacuum heat insulation material recorded in No. 2002-48466, Japanese Laid-Open Patent Publication (patent documentation 2) makes the degree of vacuum of vacuum heat insulation material be deteriorated because of the gas produced from core material or the gas of thoroughly coming in from outside, in order to suppress heat-shielding performance to be deteriorated, sorbent is encased in together with core material the inside of outsourcing material.Can use as sorbent: zeolite, active carbon; The metallic oxide such as calcium chloride, magnesium oxide; The hydroxide such as magnesium hydroxide, calcium hydroxide; The alloys such as barium-lithium alloy.
In addition, the vacuum heat insulation material that No. 2006-17169, Japanese Laid-Open Patent Publication (patent documentation 3) is recorded forms glass wool by the glass fibre as inorfil stacking material, core material is made up of this glass wool, core material reduced pressure sealing is inner at outsourcing material, and the density of the core material in vacuum heat insulation material reaches 200 ~ 270kg/m 3, open the glass fibre of length of staple more than 100 μm that the core material after outsourcing material includes more than 75%.
Patent documentation 1: No. 2002-161994, Japanese Laid-Open Patent Publication
Patent documentation 2: No. 2002-48466, Japanese Laid-Open Patent Publication
Patent documentation 3: No. 2006-17169, Japanese Laid-Open Patent Publication
Summary of the invention
But, the vacuum heat insulation material that the vacuum heat insulation material recorded as No. 2002-161994, Japanese Laid-Open Patent Publication (patent documentation 1) or Japanese Laid-Open Patent Publication 2002-48466 publication (patent documentation 2) are recorded, Improving ways in the past utilizes adsorbent moisture to suppress the interior voltage rise of vacuum heat insulation material high, but utilize above-mentioned Improving ways to be in the past limited to improve the heat-shielding performance of vacuum heat insulation material.
Therefore, the object of the present invention is to provide vacuum heat insulation material and the equipment with this vacuum heat insulation material, described vacuum heat insulation material has excellent heat-shielding performance, and this excellent heat-shielding performance can surmount in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
The present inventor is in order to solve vacuum heat insulation material Problems existing in the past, repeatedly conduct in-depth research, it found that: when the thermofussion welding portion of the outsourcing material of vacuum heat insulation material is formed by the material containing hydrocarbon, just can realize above-mentioned purpose by the inside sorbing material of adsorbed hydrocarbons gas being housed in outsourcing material.Based on above-mentioned discovery, vacuum heat insulation material of the present invention has following characteristics.
Vacuum heat insulation material of the present invention comprises: outsourcing material; Core material, is housed in the inside of outsourcing material, is laminated by multiple nonwovens; And sorbing material, be housed in the inside of outsourcing material.Nonwovens at least comprises many inorfils utilizing continuous filament method to manufacture, in nonwovens, most of inorfil in many inorfils extends on the direction substantially parallel with the surface of nonwovens, outsourcing material has thermofussion welding portion, makes to contact with each other between outsourcing material carry out thermofussion welding in this thermofussion welding portion.Thermofussion welding portion is formed by the material containing hydrocarbon.Sorbing material by the carrying of the potassium permanganate of adsorbed hydrocarbons gas on porous substrate, described appropriate hydrocarbon gas after the inner pressure relief of the described outsourcing material by containing described core material thermofussion welding portion described in thermofussion welding and seal described outsourcing material time produce from described thermofussion welding portion, and to the diffusion inside of described outsourcing material, near the described thermofussion welding portion carrying out thermofussion welding after described core material and described sorbing material are contained in described outsourcing material with decompression state, configure described sorbing material.
The present inventor has carried out various confirmatory experiment, find when the thermofussion welding portion of the outsourcing material of vacuum heat insulation material is formed by the material containing hydrocarbon, when carrying out thermofussion welding to thermofussion welding portion, harmful effect can be produced to the heat-shielding performance of vacuum heat insulation material.
Because the thermofussion welding portion of the outsourcing material to vacuum heat insulation material carries out thermofussion welding to seal, so the appropriate hydrocarbon gas produced from thermofussion welding portion during thermofussion welding not only spreads, also to the diffusion inside of the outsourcing material of vacuum heat insulation material to the outside of vacuum heat insulation material.The appropriate hydrocarbon gas being diffused into the outsourcing material inside of vacuum heat insulation material is sealed in the inside of outsourcing material.
Owing to carrying out thermofussion welding to seal to the thermofussion welding portion of the outsourcing material of vacuum heat insulation material under a reduced pressure, if so appropriate hydrocarbon gas is sealed in the inside of outsourcing material under the state of diffusion, then the degree of vacuum of outsourcing material inside reduces.Because the degree of vacuum of outsourcing material inside reduces, the heat-shielding performance of vacuum heat insulation material is caused to reduce.
Therefore, the sorbing material of adsorbed hydrocarbons gas is housed in the inside of outsourcing material, the appropriate hydrocarbon gas being diffused into outsourcing material inside is adsorbed in sorbing material.By appropriate hydrocarbon gas is adsorbed onto in sorbing material, can prevent because appropriate hydrocarbon gas causes degree of vacuum to reduce.
Thus, can provide a kind of vacuum heat insulation material with excellent adiabatic capacity, described excellent heat-shielding performance can surmount in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
The core material Problems existing that the present inventor uses to solve vacuum heat insulation material in the past, repeatedly conduct in-depth research, it found that, by making, in the fiber forming vacuum heat insulation material core material, at least to include and utilize many inorfils of continuous filament method manufacture just can realize above-mentioned purpose.Wherein, so-called continuous filament method is a kind of fibre manufacture, by carry out making molten glass flow through lining nozzle and flow out continuously, stretch, Fibrotic operation, generate continuous print fiber.Based on above-mentioned discovery, vacuum heat insulation material of the present invention preferably has following feature.
Adopt continuous filament method can producd fibers diameter difference is very little in a large number many fibers.In addition, each fiber straightness accuracy of the inorfil utilizing continuous filament method to manufacture is very high.Therefore, by utilizing many inorfils of continuous filament method manufacture to cut into substantially certain length, can under the state that straightness accuracy is very high, obtain very little and many inorfils that length is substantially identical of fiber diameter difference.
Because the nonwovens forming core material at least includes many inorfils utilizing continuous filament method to manufacture, so when using above-mentioned many inorfils to form nonwovens, if each inorfil is arranged on the direction parallel relative to the surface of nonwovens, can easily arrange many inorfils, extend on the direction substantially parallel with the surface of nonwovens to make most inorfil.Now, although the major part of many inorfils extends on the direction of the surperficial general parallel orientation with nonwovens, be not be mutually closely arranged on parallel direction, but towards random direction dispersed arrangement in the plane forming nonwoven surface.Therefore, the inorfil be filled between many inorfils forming core material can be reduced as far as possible, and the inorfil interweaved between many inorfils can be reduced, so can prevent from producing heat transfer between inorfil as far as possible.Thus, by preventing from producing heat transfer along core material thickness direction, the thermal conductivity of core material can be made to reduce, thus the vacuum heat insulation material core material with excellent adiabatic capacity can be obtained, described excellent heat-shielding performance can surmount in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
In vacuum heat insulation material of the present invention, preferably: the fiber diameter of inorfil more than 3 μm, less than 15 μm, the average fiber length of inorfil is at more than 3mm, below 15mm.In this case, the thermal conductivity of core material can be reduced to greatest extent, thus the vacuum heat insulation material with most excellent adiabatic capacity can be obtained.
In vacuum heat insulation material of the present invention, preferably: inorfil is glass fibre.In this case, such as, because other inorfils of thermal conductivity ratio of glass fibre are little, less than ceramic fiber, so the thermal conductivity by reducing raw material itself, the heat-shielding performance of core material can be improved further.
Equipment of the present invention preferably includes: outer casing; Internal box, is configured in the inner side of outer casing; And vacuum heat insulation material, between the outer box and inner box, vacuum heat insulation material comprises above-mentioned vacuum heat insulation material in configuration.
Such as, refrigerator cools the food being housed in internal box inside effectively.In addition, such as drying and washing machine, to the clothing etc. being housed in internal box inside dried object blowout hot blast, carries out drying effectively.In such devices, in order to the temperature of internal box inside is remained the set point of temperature low or higher than the external temperature of outer casing, or in order to effectively cool the inside of internal box or heat, need to make the inside of internal box and the external insulation of outer casing.Therefore, vacuum heat insulation material is configured with between the outer box and inner box.If the heat-shielding performance of configuration vacuum heat insulation material is between the outer box and inner box excellent, then owing to can reduce the energy for making the inside of internal box low or higher than the external temperature of outer casing, so can be energy-conservation.
Therefore, by making configuration vacuum heat insulation material between the outer box and inner box comprise above-mentioned vacuum heat insulation material, heat-shielding performance and the excellent equipment of energy-efficient performance can be provided.
As mentioned above, according to the present invention, can provide the vacuum heat insulation material with excellent adiabatic capacity and the equipment with this vacuum heat insulation material, described excellent heat-shielding performance can surmount in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
Accompanying drawing explanation
(A) of Fig. 1 is the front elevation of the original state representing the vacuum heat insulation material that confirmatory experiment 1 uses, (B) sectional view during vacuum heat insulation material is observed from direction shown in the B-B line of Fig. 1 (A), (C) be represent to have carried out the as-welded front elevation of second time hot melt, (D) represents to have carried out the as-welded front elevation of third time hot melt.
Fig. 2 is the figure represented because thermofussion welding number of times difference causes the thermal conductivity of vacuum heat insulation material to change.
Fig. 3 is the figure represented because thermofussion welding minister degree difference causes the thermal conductivity of vacuum heat insulation material to change.
Fig. 4 is the sectional view of the vacuum heat insulation material structure schematically illustrating first embodiment of the invention.
Fig. 5 is the stereogram schematically illustrating one embodiment of the present invention, and (A) represents the configuration of core material and outsourcing material, after (B) represents outsourcing material inner pressure relief, and the situation of vacuum heat insulation material inside.
Fig. 6 is the planimetric map of one embodiment of the present invention, the distribution of the glass fibre of the nonwovens that the core material schematically illustrating formation vacuum heat insulation material uses.
Fig. 7 is the plane electronics photomicrograph (magnification factor 100 times) representing one embodiment of the present invention, represents that the glass fibre that forms the nonwovens that the core material of vacuum heat insulation material uses is by the distribution before compressing.
Fig. 8 is the section electron micrograph (magnification factor 100 times) representing one embodiment of the present invention, represents that the glass fibre that forms the nonwovens that the core material of vacuum heat insulation material uses is by the distribution before compressing.
(A) of Fig. 9 is the cross-sectional side view of the entirety of the refrigerator representing second embodiment of the invention, and (B) represents the plan view comprising the outcase of refrigerator of a part of section.
Figure 10 is the cross-sectional side view of the entirety of the hot-water bottle representing third embodiment of the invention.
(A) of Figure 11 is the isometric front view of the entirety of the electric cooker representing four embodiment of the invention, and (B) is rear isometric view, and (C) is the figure representing the component being housed in electric cooker inside.
Figure 12 is the stereogram of the entirety of the drying and washing machine representing fifth embodiment of the invention.
Figure 13 schematically illustrates in the glass wool that in the past uses as the core material of vacuum heat insulation material, the planimetric map of the distribution of glass fibre.
Figure 14 is plane electronics photomicrograph (magnification factor 100 times), represents in the glass wool in the past used as the core material of vacuum heat insulation material, and glass fibre is by the distribution before compressing.
Figure 15 is section electron micrograph (magnification factor 100 times), represents in the glass wool in the past used as the core material of vacuum heat insulation material, and glass fibre is by the distribution before compressing.
Description of reference numerals
1 vacuum heat insulation material 100 core material
110 nonwovens 200 outsourcing materials
230 innermost layer 300 thermofussion welding portions
400 sorbing material 3 refrigerators
301 outer casing 302 internal box
320 vacuum heat insulation material 4 hot-water bottles
411 upper surface 412 lower surfaces
421 outer container 422 stored hot water containers
430 vacuum heat insulation material 5 electric cookers
501 casing 503 outer pots
510 vacuum heat insulation material 6 drying and washing machines
601 shells 603 wash dry slot container
610 vacuum heat insulation materials
Embodiment
As mentioned above, the present inventor is by carrying out various confirmatory experiment discovery: when being formed the thermofussion welding portion of outsourcing material of vacuum heat insulation material by the material containing hydrocarbon, when carrying out thermofussion welding to thermofussion welding portion, harmful effect is produced to the heat-shielding performance of vacuum heat insulation material.Below the confirmatory experiment that inventor carries out is described.
(confirmatory experiment 1)
In order to verify because of the appropriate hydrocarbon gas of outsourcing material inside amount increase and the heat-shielding performance of vacuum heat insulation material is reduced, measure the change of the heat-shielding performance of outsourcing material being carried out to the vacuum heat insulation material after repeatedly thermofussion welding.
(A) of Fig. 1 is the front elevation representing the vacuum heat insulation material original state that confirmatory experiment 1 uses, (B) sectional view during vacuum heat insulation material is observed from direction shown in the B-B line of Fig. 1 (A), (C) be represent to have carried out the as-welded front elevation of second time hot melt, (D) represents to have carried out the as-welded front elevation of third time hot melt.
As shown in (A), (B) of Fig. 1, in the vacuum heat insulation material 2 that confirmatory experiment 1 uses, core material 10 is housed in the outsourcing material 20 with barrier properties for gases being formed as bag-shaped inner, under a reduced pressure, carry out thermofussion welding to seal between thermofussion welding portion 30 and 31 pairs, thermofussion welding portion outsourcing material 20.
The outermost surface 21 of outsourcing material 20 uses nylon, mesosphere 22 use aluminium-vapour deposition PET resin and aluminium foil two-layer, innermost layer 23 uses two kinds of polyethylene resins.
Core material 10 is laminated by multiple nonwovens 11.Each layer nonwovens 11 is used as the glass fibre of one of inorfil and a small amount of organic bond, utilizes copy paper method to make.Specifically, core material 10 is made in the following way.
Fiber diameter be 10 μm, average fiber length is that the fiberglas chopped strand (be オ mono-ウ エ Application ス コ mono-ニ Application グ company (Owens Corning Corporation) manufacture) of 10mm is put in water, the concentration of fiberglas chopped strand is made to be 0.5 quality %, the エ マ ノ mono-Application (Emanon as dispersing agent of 1 mass parts is added relative to the fiberglas chopped strand of 100 mass parts, TM trade mark) 3199 (Kao Corp's manufactures), prepare fiberglas chopped strand slip by carrying out stirring.
Use the slip of the fiberglas chopped strand obtained to utilize wet type copy paper method to manufacture paper with pulp, prepare reticulated work.Dilute with water acrylic emulsion (Dainippon Ink. & Chemicals Inc manufactures GM-4), be 3.0 quality % to make the solid concentration of acrylic emulsion, make the reticulated work obtained containing in the liquid be immersed in after this dilution, and the moisture that reticulated work absorbs is adjusted, make reticulated work biodiversity be 0.7 quality % relative to glass fiber quality.After this, by making reticulated work dry, the nonwovens 11 that core material 10 uses is made.The grammes per square metre of the nonwovens 11 that the core material 10 obtained uses is 100g/m 2.Multiple nonwovens 11 stacked form core material 10.Core material 10 is of a size of that long limit is 435mm, minor face is 400mm, thickness is 9mm.
Seal outsourcing material 20 as follows.First, after thermofussion welding is carried out on three limits of the 30 pairs of outsourcing materials 20 in thermofussion welding portion, core material 10 is filled into the inside of outsourcing material 20.Then, in vacuum chamber, under a reduced pressure, thermofussion welding is carried out to the thermofussion welding portion 31 of the outsourcing material 20 being filled with core material 10.Thus, core material 10 is sealed in the inside of outsourcing material 20, thus makes vacuum heat insulation material 2.When being arranged on the Pirani vacuum gauge indicated value in vacuum chamber and reaching 0.009TOrr, at the temperature of 170 ~ 220 DEG C, thermofussion welding is carried out to thermofussion welding portion 31.Measure the thermal conductivity of the vacuum heat insulation material 2 prepared by this way.
Then, the thermofussion welding portion 32 inside thermofussion welding portion 31 carries out thermofussion welding, measures thermal conductivity equally.After this, the thermofussion welding portion 33 inside thermofussion welding portion 32 carries out thermofussion welding again, and measures thermal conductivity.The thermofussion welding carried out in thermofussion welding portion 32,33 is identical with the thermofussion welding carried out in thermofussion welding portion 31, is all to carry out at the temperature of 170 ~ 220 DEG C.
In addition, the polyethylene resin of the innermost layer 23 of outsourcing material 20 can adopt HDPE (high density polyethylene (HDPE)) and LLDPE (straight-chain low density polyethylene) these two kinds, has carried out thermal conductivity measurement thus to following two kinds of vacuum heat insulation materials: one has the vacuum heat insulation material of use HDPE (high density polyethylene (HDPE)) as the outsourcing material of hot melt layer; Another kind has the vacuum heat insulation material of use LLDPE (straight-chain low density polyethylene) as the outsourcing material of hot melt layer.Heat conductivity measuring device (Eko Instruments Trading manufactures HC-074/600) is used to carry out heat conducting coefficient measuring.The mean temperature of vacuum heat insulation material during measurement is 24 DEG C.
Fig. 2 is the figure represented because thermofussion welding number of times difference causes the thermal conductivity of vacuum heat insulation material to change.
As shown in Figure 2, when preparing vacuum heat insulation material, when carrying out thermofussion welding in thermofussion welding portion 31, HDPE is used to be 1.5 as the thermal conductivity of the vacuum heat insulation material 2 of the polyethylene resin of the innermost layer 23 of the outsourcing material 20 shown in Fig. 1.Owing to also carrying out thermofussion welding in thermofussion welding portion 32, so thermal conductivity rises to 1.7, heat-shielding performance reduces.If also carry out thermofussion welding in thermofussion welding portion 33, then thermal conductivity remains 1.7.
On the other hand, when making vacuum heat insulation material 2, when carrying out thermofussion welding in thermofussion welding portion 31, LLDPE is used to be 1.2 as the thermal conductivity of the vacuum heat insulation material of the polyethylene resin of the innermost layer 23 of outsourcing material 20.Owing to also carrying out thermofussion welding in thermofussion welding portion 32, so thermal conductivity rises to 1.3, heat-shielding performance reduces.If also carry out thermofussion welding in thermofussion welding portion 33, then thermal conductivity remains 1.3.
Can think due to after having carried out thermofussion welding in thermofussion welding portion 31, thermofussion welding portion 32 inside thermofussion welding portion 31, thermofussion welding portion 33 also carry out thermofussion welding, so the appropriate hydrocarbon gas that the polyethylene resin thermolysis of outsourcing material 20 produces is diffused into the inside of outsourcing material 20.Owing to having carried out thermofussion welding to outermost thermofussion welding portion 31, outsourcing material 20 has been sealed, so appropriate hydrocarbon gas is closed in the inside of outsourcing material 20.Therefore, the degree of vacuum of vacuum heat insulation material 2 reduces, and thermal conductivity also reduces.
(confirmatory experiment 2)
In order to verify that the appropriate hydrocarbon gas because of generation when thermofussion welding portion being carried out to thermofussion welding makes the heat-shielding performance of vacuum heat insulation material reduce further, measure the change of the heat-shielding performance of vacuum heat insulation material during the thermofussion welding length changing outsourcing material.
(A) of Fig. 1 that vacuum heat insulation material adopts above-mentioned confirmatory experiment 1 to use, the vacuum heat insulation material 2 shown in (B).Use HDPE as the polyethylene resin of the innermost layer 23 of outsourcing material 20.
In confirmatory experiment 2, first thermofussion welding is carried out to the total length in the thermofussion welding portion 31 of the vacuum heat insulation material 2 shown in (A) of Fig. 1.Measure the thermal conductivity of now vacuum heat insulation material 2.After this, open 1/5 of thermofussion welding portion 31 total length, make the internal pressure of vacuum heat insulation material 2 turn back to barometric pressure.Then, again thermofussion welding has been carried out to 1/5 part opened in thermofussion welding portion 31 under a reduced pressure.Measure the thermal conductivity of now vacuum heat insulation material 2.Measurement about the thermal conductivity to the vacuum heat insulation material carrying out thermofussion welding to seal between outsourcing material 20 is identical with confirmatory experiment 1.The total length in thermofussion welding portion 31 is 470mm.
By this twice measurement of the thermal conductivity to vacuum heat insulation material 2, the impact of the appropriate hydrocarbon gas of generation when only carrying out thermofussion welding to 1/5 length of thermofussion welding portion 31 total length, compare with the impact of the appropriate hydrocarbon gas of generation when thermofussion welding portion 31 total length being carried out to thermofussion welding, can investigate.
Fig. 3 is the figure represented because thermofussion welding minister degree difference causes the thermal conductivity of vacuum heat insulation material to change.
As shown in Figure 3, having carried out the thermal conductivity after thermofussion welding to the total length in thermofussion welding portion 31 is 1.5.And after open thermofussion welding portion 31 total length 1/5, then to carry out the thermal conductivity after thermofussion welding be 1.3.
As can be seen from the result of above confirmatory experiment 1 and confirmatory experiment 2, when carrying out thermofussion welding to seal outsourcing material to the thermofussion welding portion formed by the material containing hydrocarbon, the number of times of thermofussion welding is more, the thermal conductivity of vacuum heat insulation material is larger, in addition, the length of carrying out the thermofussion welding portion of thermofussion welding when finally sealing outsourcing material is longer, and thermal conductivity is larger.
Thus, can think: because the appropriate hydrocarbon gas of generation when the thermofussion welding portion formed by the material containing hydrocarbon being carried out to thermofussion welding is diffused into outsourcing material inside, so make the degree of vacuum of outsourcing material inside reduce, thus the heat-shielding performance of vacuum heat insulation material is reduced.
Therefore, the sorbing material of adsorbed hydrocarbons gas is housed in outsourcing material inside, the appropriate hydrocarbon gas being diffused into outsourcing material inside to be adsorbed onto in sorbing material.By appropriate hydrocarbon gas is adsorbed onto in sorbing material, can prevent because appropriate hydrocarbon gas makes degree of vacuum reduce.
As mentioned above, the present inventor finds: when the thermofussion welding portion of the outsourcing material of vacuum heat insulation material is formed by the material containing hydrocarbon, by the sorbing material of adsorbed hydrocarbons gas being housed in the inside of outsourcing material, the vacuum heat insulation material with excellent adiabatic capacity can be obtained.Based on above-mentioned discovery, vacuum heat insulation material of the present invention has following feature.
Vacuum heat insulation material of the present invention comprises: outsourcing material; Core material, is housed in the inside of outsourcing material; And sorbing material, be housed in the inside of outsourcing material.Outsourcing material has thermofussion welding portion, makes to contact with each other between outsourcing material carry out thermofussion welding in this thermofussion welding portion.Thermofussion welding portion is formed by the material containing hydrocarbon.Sorbing material energy adsorbed hydrocarbons gas.
With reference to the accompanying drawings embodiments of the present invention are described below.
(the first mode of execution)
Fig. 4 is the sectional view of the vacuum heat insulation material structure schematically illustrating first embodiment of the invention.(A) of Fig. 4 represents the state before reducing pressure to the inside of outsourcing material, and (B) of Fig. 4 represents to carry out post-decompression state to the inside of outsourcing material.
As shown in Figure 4, in vacuum heat insulation material 1, core material 100 and sorbing material 400 are housed in the inside of outsourcing material 200, and this outsourcing material 200 has barrier properties for gases and is formed as the bag-shaped of rectangular shape.Before core material 100 and sorbing material 400 are filled in outsourcing material 200, thermofussion welding is carried out on three limits in outsourcing material 200 4 limits.As described later, after being filled with core material 100 and sorbing material 400, under a reduced pressure thermofussion welding is carried out to the thermofussion welding portion 300 on a remaining limit.Near the thermofussion welding portion 300 carrying out thermofussion welding after sorbing material 400 is configured in and becomes decompression state.Sorbing material 400 also can be configured on other positions of outsourcing material 200 inside.
As shown in (A) of Fig. 4, core material 100 is laminated by multiple nonwovens 110.Each layer nonwovens 110 is used as the glass fibre of one of inorfil and a small amount of organic bond, utilizes copy paper method to make.Although tackiness agent also can use inorganic bond, if but use inorganic bond, then the bending ductility of fiber assembly is poor, namely, the bending ductility of nonwovens 110 is poor, in addition, when using as product, higher than using the cost of organic bond owing to using the cost of inorganic bond, so preferably use organic bond.In addition, the amount as far as possible controlling tackiness agent is not excessive.
Such as potassium permanganate is carried on the porous substrate such as activated alumina or zeolite or bromine is added in the porous members such as active carbon and be used as sorbing material 400.Sorbing material 400 is not limited to these, as long as can adsorbed hydrocarbons gas.
Example as outsourcing material 200 concrete structure can exemplify: make outermost surface 210 for PETG (PET) resin, uses ethylene-vinyl alcohol copolymer resin, the innermost layer 230 with aluminium-vapour deposition layer be the gas barrier film of use high-density polyethylene resin or the ldpe resin as straight-chain low density polyethylene resin in mesosphere 220; Or outermost surface 210 uses nylon, mesosphere 220 uses aluminium-vapour deposition PET resin and aluminium foil is two-layer, innermost layer 230 is the gas barrier film etc. using the ldpe resin such as high-density polyethylene resin or straight-chain low density polyethylene resin.Thermofussion welding portion 300 is formed in a part for innermost layer 230.
In addition, in order to keep the initial heat-shielding performance of vacuum heat insulation material 1 and the heat-shielding performance along with time history, preferably in vacuum heat insulation material 1 except using except sorbing material 400, also use the sorbing material such as gas adsorption material, water adsorption material.
After core material 100 and sorbing material 400 are filled into the inside of outsourcing material 200, be housed in vacuum chamber.After making outsourcing material 200 inner pressure relief to the degree of vacuum specified, between 300 pairs, thermofussion welding portion outsourcing material 200, carry out thermofussion welding.In order to keep sealing intensity, the temperature of thermofussion welding preferably 170 ~ 220 DEG C.The method of thermofussion welding has: heat conduction board sealing means, utilizes the nichrome wire be embedded in brass or heat conduction board made of copper, heat conduction board is generated heat and heat conduction, carried out thermofussion welding to seal to thermofussion welding portion 300; And impulse fusion welding mode, utilize the nichrome wire (band heater (ribbon heater)) as heater directly to add thermofussion welding to seal to thermofussion welding portion 300.Melting welding can be carried out to thermofussion welding portion 300 by above-mentioned any means.In addition, also melting welding can be carried out by additive method.If carried out thermofussion welding to thermofussion welding portion 300, then outsourcing material 200 has been sealed.
As shown in (B) of Fig. 4, after the inner pressure relief of outsourcing material 200, utilize the external pressure of outsourcing material 200 to compress core material 100, be extruded between multiple nonwovens 110 of formation core material 100 and contact.Under state after the inner pressure relief of outsourcing material 200, the density of core material 100 is at 100 ~ 400kg/m 3scope in.
Form nonwovens 110 in the above described manner, and form core material 100 stacked for nonwovens 110, then core material 100 and sorbing material 400 are configured in the inside of outsourcing material 200 and carry out reduced pressure sealing, form vacuum heat insulation material 1.
Fig. 5 is the stereogram schematically illustrating an embodiment of the invention, and (A) represents the configuration of core material and outsourcing material, after (B) expression is reduced pressure to the inside of outsourcing material, and the state of vacuum heat insulation material inside.Illustrate only a part for each nonwovens, core material, outsourcing material respectively.
As shown in (A) of Fig. 5, stacked for multiple nonwovens 110, form core material 100.Core material 100 is covered by outsourcing material 200.Outsourcing material 200 has barrier properties for gases and is formed as bag-shaped, covers whole core material 100.
As shown in (B) of Fig. 5, if reduced pressure to the inside of bag-shaped outsourcing material 200, then core material 100 is compressed.If core material 100 is compressed, then mutually extrude between multiple nonwovens 110 and contact.
The nonwovens 110 of core material 100 can be formed by utilizing the glass fibre of continuous filament method manufacture or be formed by glass wool.
The present inventor is in order to improve the heat-shielding performance of the vacuum heat insulation material of said structure, conduct in-depth research, it found that by using the nonwovens be made up of the inorfil with specified conditions as core material, significantly improves the heat-shielding performance of vacuum heat insulation material.
Therefore, in the present embodiment, as shown in Figure 4, form the nonwovens 110 of the core material 100 that vacuum heat insulation material 1 of the present invention uses, at least include many inorfils utilizing continuous filament method to manufacture.
Inorfil can exemplify glass fibre, ceramic fiber, rock wool fibers etc., in order to form core material of the present invention, need the fiber that diameter is thin, from producing the thin fiber of described diameter in a large number can consider with the angle of lower price circulation and consider from the angle that the thermal conductivity of raw material itself is little, inorfil preferably uses glass fibre.
In the preferred mode of execution of the present invention, the core material using the glass fibre cutting into certain length, the nonwovens utilizing wet type copy paper method to manufacture as vacuum heat insulation material is used.Wherein, the glass fibre that what is called cuts into certain length refers to: utilize continuous filament method that molten glass is shaped from multiple nozzle pull-out, the glass fibre as thread continuous fiber of the even thickness after hundreds of ~ thousands of shapings is tied together and is wound in precursor, utilize guillotine cutting machine etc. that this precursor is cut into specific length.The precursor cutting into the glass fibre after specific length is like this called fiberglas chopped strand.
Because the glass fibre obtained like this is, with certain size, continuous fiber is cut into specific length, thus this glass fibre to be straightness accuracy high and the fiber that rigidity is large, and there is the fiber diameter of general uniform and be roughly circular section.That is, adopt continuous filament method can producd fibers diameter difference is very little in a large number many fibers.In addition, each fiber straightness accuracy of the inorfil utilizing continuous filament method to manufacture is very high.Therefore, by utilizing many inorfils of continuous filament method manufacture to cut into substantially certain length, can under the state that straightness accuracy is very high, obtain making fiber diameter difference very little and substantially identical many inorfils of length.
Thus, when using this glass fibre to utilize wet type copy paper method to manufacture nonwovens, following nonwovens can be obtained: namely, although fiber extends on the direction of the surperficial general parallel orientation with nonwovens, fiber orientation random direction dispersed arrangement in the plane forming nonwoven surface.
Fig. 6 is the planimetric map of one embodiment of the present invention, the distribution of the glass fibre of the nonwovens that the core material schematically illustrating formation vacuum heat insulation material uses.Fig. 6 represents the nonwovens be made up of layer glass layer of fibers.Fig. 7 is the plane electronics photomicrograph (magnification factor 100 times) representing one embodiment of the present invention, its represents that the glass fibre that forms the nonwovens that the core material of vacuum heat insulation material uses is by the distribution before compressing, and Fig. 8 is the section electron micrograph (magnification factor 100 times) representing same distribution state.
As shown in Figure 6, many the glass fibres 111 forming upper strata and many glass fibres 112 forming lower floor extend on the direction of the surperficial general parallel orientation with nonwovens 110, but be not be mutually arranged closely on parallel direction, but towards random direction dispersed arrangement in the plane forming nonwoven surface.In addition, as shown in Figure 7, Figure 8, can find out that the straightness accuracy of each fiber is very high.Further, although most fiber extends on the direction of the surperficial general parallel orientation with nonwovens, they formed nonwoven surface plane in towards random direction dispersed arrangement.
As mentioned above, because the nonwovens 110 forming core material of the present invention at least includes many glass fibres as one of inorfil utilizing continuous filament method to manufacture, so when using above-mentioned many glass fibres to form nonwovens 110, if make each glass fibre be arranged on the direction parallel relative to the surface of nonwovens 110, then can easily arrange many glass fibres, extend on the direction of the surperficial general parallel orientation with nonwovens to make most glass fibre 111,112.Now, although the major part of many glass fibres 111,112 extends on the direction of the surperficial general parallel orientation with nonwovens 110, but be not be mutually arranged closely on parallel direction, but towards random direction dispersed arrangement in the plane forming nonwovens 110 surface.Owing to can reduce the glass fibre be filled between many glass fibres forming core material as far as possible, and the glass fibre interweaved between many glass fibres can be reduced, so can prevent from producing heat transfer between glass fibre as far as possible.Therefore, by preventing from producing heat transfer along core material thickness direction, the thermal conductivity of core material can be made to reduce, thus can obtain having the vacuum heat insulation material core material of excellent adiabatic capacity and there is the vacuum heat insulation material of this core material, described excellent heat-shielding performance can surmount in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
Be not particularly limited the composition of glass fibre, C glass, D glass, E glass etc. can be used, but calm facile angle set out, preferably adopt E glass (aluminium borosilicate glass).
As mentioned above, the core material of present embodiment is made up of nonwovens 110, the inorfil forming this nonwovens 110 is the glass fibre with specific length that continuous fiber is cut off with given size, and this glass fibre straightness accuracy is very high and have and be roughly circular section.Therefore, as long as be not side by side parallel arrangement towards a large amount of glass fibres of random direction dispersion, be then point cantact between each bar glass fibre, so the heat transfer between glass fibre significantly can be suppressed.
Although also can consider to use other raw material to carry out alternative glass fibre, the general inorganic fibers such as the alumina fibre chopped strand of alumina fibre that use are more expensive than glass fibre, and thermal conductivity is high, so be not preferred material.
In addition, the thermal conductivity of organic material is generally low than inorganic material, but does not have rigidity.Therefore, organic fibrous material makes fibre deformation at the position of fiber crossovers because of external pressure, causes the face contact between fiber or the minimizing of vacuum space ratio.Its result, core material use organic fiber vacuum heat insulation material due to thermal conductivity high, so be not preferred material.
As the manufacture method of core material 100, first, at least use utilizes many of the continuous filament method manufacture glass fibres as one of inorfil, utilizes wet type copy paper method to manufacture nonwovens 110.Thus, the most of glass fibre 111,112 in many glass fibres is made to extend on the direction of the surperficial general parallel orientation with the nonwovens 110 manufactured.Then, stacked for multiple nonwovens 110.
In addition, in a mode of execution of the manufacture method of vacuum heat insulation material 1 of the present invention, first, at least use utilizes many glass fibres of continuous filament method manufacture, utilizes wet type copy paper method to manufacture nonwovens 110.Thus, make the direction of the surperficial general parallel orientation of the nonwovens 110 of the most of glass fibre 111,112 in many glass fibres and manufacture extends.Then, stacked for multiple nonwovens 110.After this, multiple nonwovens 110 after stacked are housed in the inside of outsourcing material 200, and make outsourcing material 200 inside remain in decompression state.
In a mode of execution of the manufacture method of vacuum heat insulation material 1, at least use many glass fibres utilizing continuous filament method to manufacture.When using above-mentioned many glass fibres to utilize wet type copy paper method to manufacture nonwovens 110, if make each glass fibre be arranged on the direction parallel relative to the surface of nonwovens 110, then can easily arrange many glass fibres, extend on the direction of the surperficial general parallel orientation with nonwovens 110 to make most glass fibre 111,112.Now, although the major part of many glass fibres 111,112 extends on the direction of the surperficial general parallel orientation with nonwovens 110, but be not be mutually arranged closely on parallel direction, but towards random direction dispersed arrangement in the plane forming nonwovens 110 surface.Therefore, even if in order to form core material 100 and multiple nonwovens 110 stacked, owing to can reduce the glass fibre be filled between many glass fibres as far as possible, and the glass fibre interweaved between many glass fibres can be reduced, so also can prevent from producing heat transfer between glass fibre as far as possible.Further, by multiple stacked nonwovens 110 being housed in the inside of outsourcing material 200, and making the inside of outsourcing material 200 remain in decompression state, vacuum heat insulation material 1 can be manufactured.Thus, by preventing from producing heat transfer along core material thickness direction, the thermal conductivity of core material 100 can be made to reduce, thus can obtain that there is the core material 100 of excellent adiabatic capacity and the vacuum heat insulation material 1 with this core material 100, described excellent heat-shielding performance can surmount in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
Wet type copy paper method is utilized to manufacture the nonwovens 110 be made up of glass fibre used in the present invention.In wet type copy paper method, by adding suitable dispersing agent, making the fiberglas chopped strand monofilament cutting off glass fibre with certain length, and being distributed layered, the nonwovens 110 be made up of stranded less glass fibre can be obtained.Therefore, the quantity of parallel glass fibre is side by side considerably less, and most glass fibre 111,112 is point cantact between adjacent fiber.Like this, in a thickness direction there is high compression-strength and the low-down nonwovens 110 of thermal conductivity, so above-mentioned nonwovens 110 is suitable as the core material 100 of vacuum heat insulation material 1 very much owing to producing.
In the manufacture method of vacuum heat insulation material 1, adopt wet type copy paper method to manufacture paper with pulp to nonwovens 110, this is manufactured paper with pulp and can use the paper making machine that fourdrinier paper machine, short net paper making machine, tiltedly net formula paper making machine etc. are known.
Usually, the nonwovens be made up of glass fibre is as having the thermal-protective material of heat resistance, the thermal-protective material with refractory nature or electrical insulator.Therefore, because nonwovens needs to have the intensity can born and pull open or puncture and wait, thus between fiber mostly needs be interweaved.The nonwovens be made up of glass fibre for such use utilizes copy paper method manufacture to form mostly, and this copy paper method uses fourdrinier paper machine, short net paper making machine.
And the nonwovens 110 be made up of glass fibre that vacuum heat insulation material 1 uses is housed in the inside of outsourcing material 200 as core material 100, so not too require the intensity of cloth.In addition, because the copy paper method easily making fiber direction consistent makes the area of contact between fiber increase, so for the manufacture nonwovens 110 be made up of glass fibre used in the present invention, be not preferred.On the other hand, in order to improve the heat-shielding performance of thickness direction, it is desirable to be interweaved between glass fibre less.
Therefore, as the paper making machine that the nonwovens 110 be made up of glass fibre used vacuum heat insulation material 1 is manufactured paper with pulp, applicable use may carry out the oblique net formula paper making machine of copy paper with low input (inlet) concentration, but is not be defined in this.
The fiberglas chopped strand as one of inorfil that vacuum heat insulation material 1 uses is preferably: fiber diameter is 3 ~ 15 μm, length of staple is that the component ratio of the glass fibre of 3 ~ 15mm is more than 99%.
As described below, fiber diameter can be predicted and be less than the fiberglas chopped strand that 3 μm or length of staple be less than 3mm, not be suitable for the nonwovens 110 of the core material 100 forming vacuum heat insulation material 1.
The glass fibre that fiber diameter is less than 3 μm is little due to the rigidity of fiber, when utilizing wet type copy paper method to manufacture nonwovens, producing fiber bending and being mutually wound around between fiber, the area of contact between fiber is increased.Therefore heat transfer increases, and causes the heat-shielding performance of core material to be deteriorated, so the glass fibre that fiber diameter is less than 3 μm is not preferred.
When utilizing wet type copy paper method and manufacture nonwovens with the glass fibre that length of staple is less than 3mm, time on the fiber dispersion making to be positioned at upper strata to the fiber disperseed being positioned at lower floor, the fiber on upper strata can not overlap with the fiber of lower floor, add top fiber and be bearing in possibility on lowermost fibre with a bit, such as it is contemplated that one end of top fiber hangs down into lower floor, the other end is located in the mode outstanding to thickness direction.Like this, when certain fiber becomes the state of through-thickness overlap joint between many fibers, the length direction along fiber produces heat transfer, and the area of contact between fiber increases.Heat transfer increases thus, the heat-shielding performance of core material is deteriorated, so the glass fibre that length of staple is less than 3mm is not preferred.
If use the glass fibre of fiber diameter more than 15 μm to form nonwovens, and multiple nonwovens are carried out stackedly forming core material, then the core material fiber number of plies in a thickness direction reduces, heat conduction path on thickness direction is shortened, and when forming nonwovens, emptying aperture diameter becomes large.Therefore, owing to being subject to the impact of gas on thermal conductivity, the heat-shielding performance of core material is reduced, so the glass fibre of fiber diameter more than 15 μm is not preferred.
If use length of staple at the glass fibre of more than 15mm, then because length of staple is excessive relative to fiber diameter, so the rigidity of fiber reduces and easily bends, and produce being interweaved between fiber, the area of contact between fiber is increased.Therefore, heat transfer increases, and the heat-shielding performance of core material is deteriorated, so length of staple is not preferred at the glass fibre of more than 15mm.
The core material of vacuum heat insulation material of the present invention use by the nonwovens that glass fibre is formed, do not deposit combination force between the fibers.Therefore, in order to prevent glass fibre from coming off in the manufacturing process of nonwovens, and in order to prevent shape at random in the manufacturing procedure of subsequent handling, need to use organic bond in copy paper operation.But, because nonwovens will be wrapped in inside by outsourcing material as the core material of vacuum heat insulation material, so need the use amount of organic bond to be restricted to bottom line.By the binder content in the nonwovens that glass fibre is formed preferably at below 15 quality %.
Generally use sprayer etc. the fluid binder such as resin emulsion, resin aqueous solution atomisation as organic bond, add in glass fibre.
The grammes per square metre of the nonwovens be made up of glass fibre that vacuum heat insulation material core material of the present invention uses, preferably 30 ~ 600g/m 2.30g/m is less than in the grammes per square metre of nonwovens 2in situation, because the aperture diameter existed in nonwovens is large, so the impact of gas on thermal conductivity is large.Therefore, the heat-shielding performance of core material reduces, and the intensity of core material diminishes, so the grammes per square metre of nonwovens is less than 30g/m 2be not preferred.On the other hand, if the grammes per square metre of nonwovens is more than 600g/m 2, then because drying efficiency when using glass fibre manufacture nonwovens reduces, and productivity reduces, so be not preferred.
So-called grammes per square metre generally refers to the unit of measurement of paper thickness, represents the quality of the paper of every square metre, also referred to as the weight of every square metre.Unit herein as metering nonwoven thickness uses grammes per square metre, and this nonwovens is formed by utilizing the glass fibre of wet type copy paper method manufacture.
Such as in the record of No. 2006-17169, Japanese Laid-Open Patent Publication (patent documentation 3), the average diameter preferably forming the inorfils such as the glass wool of vacuum heat insulation material core material is 1 ~ 5 μm.And record, if the average diameter of this inorfil is more than 5 μm, then the heat-shielding performance of the vacuum heat insulation material finally obtained itself reduces.The diameter forming the inorfil of core material is less, really more can improve the heat-shielding performance of vacuum heat insulation material.But thin inorfil price is high, and when utilizing wet type copy paper method to manufacture nonwovens, there is the shortcoming that dewatering efficiency reduces, productivity reduces.In contrast, for the adhering state between the fiber parameters such as fiber diameter, length of staple of inorfil and fiber, by selecting the optimum condition for improving heat-shielding performance, even if adopt the larger fiberglas chopped strand of fiber diameter as an example of inorfil, the vacuum heat insulation material of heat-shielding performance far above vacuum heat insulation material in the past also can be obtained.
In addition, even if use the fiberglas chopped strand that fiber diameter is less than 6 μm, the increase rate of the vacuum heat insulation material heat-shielding performance finally obtained is compared with the situation of the fiberglas chopped strand of use fiber diameter 10 μm, also almost negligible.Therefore, consider from productivity, price, aspect of performance, the fiber diameter of fiberglas chopped strand preferably 6 ~ 15 μm.When using the glass fibre of this scope, the vacuum heat insulation material that heat-shielding performance is higher than vacuum heat insulation material in the past can be obtained with suitable manufacture cost.
Use the core material with above-mentioned feature, utilize known method can manufacture vacuum heat insulation material of the present invention.Representative method is: in the structure of the vacuum heat insulation material 1 shown in Fig. 4, core material 100 and sorbing material 400 is housed in the outsourcing material 200 with barrier properties for gases being formed as bag-shaped inner.Accommodate the outsourcing material 200 of core material 100 under a reduced pressure and there is high gas-obstructing character, and there is the protective layer that hot sealing layer and fracture etc. carry out protecting, can make for a long time to keep decompression state in outsourcing material 200.In addition, also multiple pellicular cascades with above-mentioned characteristic can be used as outsourcing material 200.
Before carrying out above-mentioned vacuum seal, by removing or reduce the organic bond of core material, heat-shielding performance can be improved further.When using the thermosetting resin adhesives such as acrylic resin at tackiness agent, the method for thermolysis can be utilized to remove tackiness agent.
That is, before core material is sealing into outsourcing material inside, by the heat decomposition temperature of specific viscosity mixture high and than the low-melting temperature of glass fibre under process, thermolysis can be utilized only binder removal.In addition, when using the water-soluble resin tackiness agents such as PVA as tackiness agent, in addition to the method described above, can remove by utilizing warm water etc. to carry out cleaning or reduce tackiness agent.
As mentioned above, vacuum heat insulation material 1 of the present invention comprises: outsourcing material 200; Core material 100, is housed in the inside of outsourcing material 200; And sorbing material 400, be housed in the inside of outsourcing material 200.Outsourcing material 200 has thermofussion welding portion 300, makes to contact with each other between outsourcing material 200 to carry out thermofussion welding in this thermofussion welding portion 300.Thermofussion welding portion 300 is formed by the material containing hydrocarbon.Sorbing material 400 can adsorbed hydrocarbons gas.
When the thermofussion welding portion 300 of the outsourcing material 200 of vacuum heat insulation material 1 is formed by the material containing hydrocarbon, when carrying out thermofussion welding to thermofussion welding portion 300, produce appropriate hydrocarbon gas.Because the thermofussion welding portion 300 of the outsourcing material 200 to vacuum heat insulation material 1 carries out thermofussion welding to seal, so the appropriate hydrocarbon gas produced from thermofussion welding portion 300 during thermofussion welding not only spreads to the outside of vacuum heat insulation material 1, and the diffusion inside of outsourcing material 200 to vacuum heat insulation material 1.The appropriate hydrocarbon gas being diffused into outsourcing material 200 inside of vacuum heat insulation material 1 is sealed in the inside of outsourcing material 200.
Owing to carrying out thermofussion welding to seal to the thermofussion welding portion 300 of the outsourcing material 200 of vacuum heat insulation material 1 under a reduced pressure, if so seal under the state being diffused into outsourcing material 200 inside in appropriate hydrocarbon gas, then the degree of vacuum of outsourcing material 200 inside reduces.Because the degree of vacuum of outsourcing material 200 inside reduces, the heat-shielding performance of vacuum heat insulation material 1 is caused to reduce.
Therefore, the sorbing material 400 of adsorbed hydrocarbons gas is housed in the inside of outsourcing material 200, the appropriate hydrocarbon gas being diffused into outsourcing material 200 inside is adsorbed in sorbing material 400.By appropriate hydrocarbon gas being adsorbed onto in sorbing material 400, can prevent because appropriate hydrocarbon gas causes degree of vacuum to reduce.
In this way, can provide the vacuum heat insulation material 1 with excellent adiabatic capacity, described excellent heat-shielding performance can surmount in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
(the second mode of execution)
(A) of Fig. 9 is the cross-sectional side view of the entirety of the refrigerator representing second embodiment of the invention, and (B) represents the plan view comprising the outcase of refrigerator of a part of section.
As shown in (A) of Fig. 9, refrigerator 3 comprises; Outer casing 301, internal box 302, door 303, dividing plate 304, the machine room 306 of configuration compressor 305, cooling part 307, vacuum heat insulation material 320.Outer casing 301 and internal box 302 form the shell 308 of refrigerator 3.Shell 308 is formed as the cardinal principle rectangular shape of an opening.Door 303 is utilized to carry out the opening portion of switch housing 308.Utilize dividing plate 304 that the inside of shell 308 is divided into multiple room.In the present embodiment, the inside of shell 308 is such as divided into cold storage room 311, ice making compartment 312, ice storage chamber 313, refrigerating chamber 314 and vegetable compartment 315.
Vacuum heat insulation material 320 is configured with between outer casing 301 and internal box 302.In addition, vacuum heat insulation material 320 is also configured with in the inside of door 303.Being formed by the vacuum heat insulation material of the first mode of execution at least partially in the vacuum heat insulation material 320 shown in Fig. 9.
In refrigerator in the past, thermal-protective material uses hard polyurethane foams.In this refrigerator in the past, in the space formed by internal box and outer casing, injecting blown polyurethane materials, carrying out filling with insulation material by utilizing chemical reaction foaming.
By the vacuum heat insulation material replacing to the first good mode of execution of heat-shielding performance at least partially by using the thermal-protective material of hard polyurethane foams in refrigerator in the past, the lower thickness of thermal-protective material can be made pro rata with effect of heat insulation.If the lower thickness of thermal-protective material can be made, then do not make refrigerator become large, just can expand internal capacity.In addition, can realize energy-conservation.Further, due to the use amount of hard polyurethane foams can be reduced, so also easily carry out recycling when refrigerator is discarded.
The allocation position of the vacuum heat insulation material 320 shown in Fig. 9 is examples.Vacuum heat insulation material 320 also can be configured on other positions.
As mentioned above, refrigerator 3 of the present invention comprises: outer casing 301; Internal box 302, is configured in the inner side of outer casing 301; And vacuum heat insulation material 320, be configured between outer casing 301 and internal box 302, vacuum heat insulation material 320 comprises the vacuum heat insulation material of the first mode of execution.
In refrigerator 3, the food being housed in internal box 302 inside is cooled.Therefore, in refrigerator 3, need the temperature of internal box 302 inside is remained lower than the temperature of outer casing 301 outside or needs effectively to cool the inside of internal box 302.Therefore, between outer casing 301 and internal box 302, vacuum heat insulation material 320 is configured with.If the heat-shielding performance being configured in the vacuum heat insulation material 320 between outer casing 301 and internal box 302 is excellent, then can reduce the energy for making the temperature of internal box 302 inside low or higher than the temperature of outer casing 301 outside, so can be energy-conservation.
Therefore, by the vacuum heat insulation material making the vacuum heat insulation material 320 be configured between outer casing 301 and internal box 302 include the first mode of execution, heat-shielding performance and the excellent refrigerator 3 of energy-efficient performance can be provided.
(the 3rd mode of execution)
Figure 10 is the cross-sectional side view of the entirety of the hot-water bottle representing third embodiment of the invention.
As shown in Figure 10, in the inside of the lid 410 of hot-water bottle (kettle) 4 and be configured with vacuum heat insulation material 430 between stored hot water container 422 and outer container 421.Vacuum heat insulation material 430 is vacuum heat insulation materials of the first mode of execution.The component of the upper surface 411 of formation lid 410 and outer container 421 are examples for outer casing, and the component of the lower surface 412 of formation lid 410 and stored hot water container 422 are examples for internal box.In addition, the allocation position of vacuum heat insulation material 430 is examples, and vacuum heat insulation material 430 also can be configured on other positions.
In this hot-water bottle 4, have water in the interior reservoir of stored hot water container 422, this water is by heating such as resistance heating formula heater 440 grade.In addition, can the water being stored in stored hot water container 422 inside be incubated.
Thus, by using the vacuum heat insulation material of the first mode of execution in the outside of stored hot water container 422, the Thickness Ratio of thermal-protective material can be made in the past thin, described stored hot water container 422 heats water for utilizing resistance heating formula heater 440 grade, so the internal capacity of hot-water bottle 4 can be expanded, and space can be saved.In addition, the thermal insulation property of hot-water bottle 4 can be improved, and realize energy-conservation.In addition, with such as use polyurethane foam as thermal-protective material situation compared with, easily carry out the recycling of thermal-protective material.
(the 4th mode of execution)
(A) of Figure 11 is the isometric front view of the entirety of the electric cooker representing four embodiment of the invention, and (B) is rear isometric view, and (C) is the figure of the component being housed in electric cooker inside.
As shown in figure 11, electric cooker 5 is made up of casing 501 and upper cover 502, and this upper cover 502 is for the opening portion on switch casing 501 top.As shown in (C) of Figure 11, have in casing 501 internal configurations: interior pot 504; Heater 505, is configured in the bottom of interior pot 504; And outer pot 503, pot 504 and heater 505 in covering.In the inside of the upper cover 502 of electric cooker 5 and be configured with vacuum heat insulation material 510 between outer pot 503 and casing 501.Vacuum heat insulation material 510 is configured to the outer circumferential face of covering outer pot 503 and is wrapped on the outer circumferential face of outer pot 503.Vacuum heat insulation material 510 is vacuum heat insulation materials of the first mode of execution.
Casing 501 is examples for outer casing, and outer pot 503 is examples for internal box.In addition, the upper surface of upper cover 502 is examples for outer casing, and the lower surface of upper cover 502 is examples for internal box.The allocation position of vacuum heat insulation material 510 is examples, and vacuum heat insulation material 510 also can be configured on other positions.
By configuring vacuum heat insulation material 510 in the periphery of outer pot 503, described outer pot 503 accommodates the interior pot 504 as the portion of cooking, and can obtain the heat-shielding performance identical with thermal-protective material in the past, and the Thickness Ratio of thermal-protective material can be made in the past thin.Thus, space, energy-conservation can be saved, and jumbo electric cooker 5 can be obtained.
In addition, due to by the periphery of outer pot 503 configuration vacuum heat insulation material 510, make the temperature of interior pot 504 from being configured with the bottom of heater 505 along the distribution of short transverse isothermal, so convection current can be produced equably in interior pot 504.
(the 5th mode of execution)
Figure 12 is the stereogram of the entirety of the drying and washing machine representing fifth embodiment of the invention.
As shown in figure 12, drying and washing machine 6 comprises: shell 601; Lid 602, for the opening portion of switch housing 601; Washing dry slot container 603, is housed in the inside of shell 601; And washing dry slot (not shown), be housed in the inside of washing dry slot container 603.Vacuum heat insulation material 610 is configured with between shell 601 and washing dry slot container 603.Vacuum heat insulation material 610 is vacuum heat insulation materials of the first mode of execution.Drying and washing machine 6 is the washing machines with drying function.The allocation position of vacuum heat insulation material 610 is examples, and vacuum heat insulation material 610 also can be configured on other positions.
Washing dry slot can be supported in the inside of washing dry slot container 603 rotationally.User puts into the inside of washing dry slot dried objects such as clothings, by operating the operation unit be configured on lid 602, washs and drying to dried object.When washing dried object, at the interior reservoir water of washing dry slot, and dropping into washing agent, by making washing dry slot rotate, cleaning dried object.When carrying out drying to dried object, by providing hot blast in a looping fashion to the inside of washing dry slot, drying is carried out to dried object.
By vacuum heat insulation material 610 being wrapped on the outer circumferential face of washing dry slot container 603, the temperature of the hot blast at washing dry slot Inner eycle can be made to be not easy to decline, so effectively drying can be carried out.
Embodiment
One of effect of vacuum heat insulation material of the present invention to obtain excellent heat-shielding performance.To change outsourcing material, core material, sorbing material kind and the thermal conductivity of vacuum heat insulation material prepared is measured, and compare heat-shielding performance.
The vacuum heat insulation material that the present embodiment uses is the same with the vacuum heat insulation material of the first mode of execution, is core material and sorbing material to be housed in be formed as the bag-shaped outsourcing material inside with barrier properties for gases.After thermofussion welding portion has carried out thermofussion welding to three of the outsourcing material of cardinal principle rectangular shape limits, core material and sorbing material have been filled in the inside to outsourcing material.In vacuum chamber, under a reduced pressure, thermofussion welding is carried out to the thermofussion welding portion of the outsourcing material being filled with core material and sorbing material.Thus, core material is sealed in the inside of outsourcing material, makes vacuum heat insulation material.When being arranged on the Pirani vacuum gauge indicated value in vacuum chamber and reaching 0.009Torr, at the temperature of 170 ~ 220 DEG C, thermofussion welding is carried out to thermofussion welding portion.
As outsourcing material, the gas barrier film that outermost surface uses nylon, mesosphere uses aluminium-vapour deposition PET resin and aluminium foil is two-layer, innermost layer is use polyethylene resin.Innermost layer as outsourcing material uses LLDPE or HDPE.
Core material is laminated by multiple nonwovens.Core material uses wet type copy paper core material or glass wool core material.Specifically, wet type copy paper core material and glass wool core material are made respectively as follows.
(1) wet type copy paper core material
In wet type copy paper core material, each nonwovens is used as the glass fibre of one of inorfil and a small amount of organic bond, utilizes copy paper method to make.
Fiber diameter be 10 μm, average fiber length is that the fiberglas chopped strand (be オ mono-ウ エ Application ス コ mono-ニ Application グ company (Owens Corning Corporation) manufacture) of 10mm is put in water, the concentration of fiberglas chopped strand is made to be 0.5 quality %, the エ マ ノ mono-Application (Emanon as dispersing agent of 1 mass parts is added relative to the fiberglas chopped strand of 100 mass parts, TM trade mark) 3199 (Kao Corp's manufactures), prepare fiberglas chopped strand slip by carrying out stirring.
Use the slip of the fiberglas chopped strand obtained to utilize wet type copy paper method to manufacture paper with pulp, prepare reticulated work.Dilute with water acrylic emulsion (Dainippon Ink. & Chemicals Inc manufactures GM-4), be 3.0 quality % to make the solid concentration of acrylic emulsion, make the reticulated work obtained containing in the liquid be immersed in after this dilution, and the moisture that reticulated work absorbs is adjusted, make reticulated work biodiversity be 0.7 quality % relative to glass fiber quality.After this, by making reticulated work dry, the nonwovens that wet type copy paper core material uses is made.The grammes per square metre of the nonwovens that the wet type copy paper core material obtained uses is 100g/m 2.
Multiple nonwovens stacked form wet type copy paper core material.Wet type copy paper core material is of a size of: long limit is 435mm, minor face is 400mm, thickness is 9mm.
(2) glass wool core material
Stacked fiber diameter is the aggregate that the glass wool of 3.5 μm is used as glass fibre, and by carrying out the hot press-formed density for regulation, makes tabular core material.Glass wool core material is of a size of: long limit is 435mm, minor face is 400mm, thickness is 8mm.
Figure 13 schematically illustrates in the glass wool that in the past uses as the core material of vacuum heat insulation material, the planimetric map of the distribution of glass fibre.Figure 14 is plane electronics photomicrograph (magnification factor 100 times), represent in the glass wool in the past used as the core material of vacuum heat insulation material, glass fibre is by the distribution before compressing, and Figure 15 is the section electron micrograph (magnification factor 100 times) representing same distribution state.
As shown in figure 13, can find out in glass wool 800, many glass fibres 810 of various length of staple extend and random distribution to all directions.In addition, as shown in Figure 14, Figure 15, in the glass wool utilizing flame method or centrifuge method to manufacture, length of staple has been mixed at the short fibre of below 1mm and the microfibre of fiber diameter below 1 μm relative to main fibre.Can think: be filled between main fibre due to above-mentioned short fibre or microfibre or interweave between main fibre, producing heat transfer between the fibers, cause the heat transfer along core material thickness direction, so make heat-shielding performance reduce.In addition, can find out in above-mentioned glass wool, main fibre also includes fiber that is a large amount of bending or distortion.
Sorbing material can be used alone or in combination following three kinds.
(1) calcium oxide (CaO), 10g
(2) appropriate hydrocarbon gas sorbing material A: the PurafilSelect being main component with aluminium oxide and potassium permanganate (Co., Ltd. ジ エ イ エ system エ ス (JMS) manufacture), 2.5g
(3) appropriate hydrocarbon gas sorbing material B: サ エ ス ゲ Star タ mono-(Saes getters company manufactures SG-CONB03), 10g.Appropriate hydrocarbon gas sorbing material B contains calcium oxide (50 ~ 100%), cobalt oxide (10 ~ 25%), barium (less than 2.5%), lithium (less than 2.5%).
The potassium permanganate of appropriate hydrocarbon gas sorbing material A adsorbs the ethene as appropriate hydrocarbon gas.In addition, the cobalt oxide adsorbed hydrocarbons gas of appropriate hydrocarbon gas sorbing material B.On the other hand, calcium oxide not adsorbed hydrocarbons gas and hygroscopic moisture.
Above outsourcing material, core material and the sorbing material mode by following (1) ~ (8) is combined, makes eight kinds of vacuum heat insulation materials.
(1) innermost layer uses the outsourcing material formed by LLDPE.Core material uses wet type copy paper core material.Sorbing material uses calcium oxide (CaO).
(2) innermost layer uses the outsourcing material formed by LLDPE.Core material uses wet type copy paper core material.Sorbing material uses calcium oxide (CaO) and appropriate hydrocarbon gas sorbing material A.
(3) innermost layer uses the outsourcing material formed by LLDPE.Core material uses wet type copy paper core material.Sorbing material uses appropriate hydrocarbon gas sorbing material B.
(4) innermost layer uses the outsourcing material formed by HDPE.Core material uses wet type copy paper core material.Sorbing material uses calcium oxide (CaO).
(5) innermost layer uses the outsourcing material formed by HDPE.Core material uses wet type copy paper core material.Sorbing material uses calcium oxide (CaO) and appropriate hydrocarbon gas sorbing material A.
(6) innermost layer uses the outsourcing material formed by HDPE.Core material uses wet type copy paper core material.Sorbing material uses appropriate hydrocarbon gas sorbing material B.
(7) innermost layer uses the outsourcing material formed by HDPE.Core material uses glass wool core material.Sorbing material uses calcium oxide (CaO).
(8) innermost layer uses the outsourcing material formed by HDPE.Core material uses glass wool core material.Sorbing material uses calcium oxide (CaO) and appropriate hydrocarbon gas sorbing material A.
Measure the thermal conductivity of the eight kinds of vacuum heat insulation materials in (1) ~ (8).Thermal conductivity uses heat conductivity measuring device (Eko Instruments Trading manufactures HC-074/600) to measure.The mean temperature of vacuum heat insulation material during measurement is 24 DEG C.
The thermal conductivity obtained is as shown in table 1.
Table 1
As shown in table 1, if use to innermost layer the outsourcing material that formed by LLDPE and core material uses (1) ~ (3) of the vacuum heat insulation material of wet type copy paper core material to compare, compared with (1) that then uses calcium oxide (CaO) with sorbing material, use (2) of calcium oxide and appropriate hydrocarbon gas sorbing material A and use the thermal conductivity reduction of (3) of appropriate hydrocarbon gas sorbing material B.
In addition, if use to innermost layer the outsourcing material that formed by HDPE and core material uses (4) ~ (6) of the vacuum heat insulation material of wet type copy paper core material to compare, compared with (4) that then use calcium oxide (CaO) with sorbing material, use (5) of calcium oxide and appropriate hydrocarbon gas sorbing material A and use the thermal conductivity reduction of (6) of appropriate hydrocarbon gas sorbing material B.
In addition, if use to innermost layer the outsourcing material that formed by HDPE and core material uses (7) and (8) of the vacuum heat insulation material of glass wool core material to compare, compared with (7) that then use calcium oxide (CaO) with sorbing material, the thermal conductivity of (8) of calcium oxide and appropriate hydrocarbon gas sorbing material A is used to reduce.
This shows, have vacuum heat insulation material (2) (3) (5) (6) (8) of the appropriate hydrocarbon gas sorbing material A with appropriate hydrocarbon gas sorbing material B of adsorbed hydrocarbons gas, with do not have adsorbed hydrocarbons gas sorbing material vacuum heat insulation material (1) (4) (7) compared with, thermal conductivity is little, there is excellent heat-shielding performance, and described excellent heat-shielding performance surmounts in the past to any improvement that thermal insulation the subject of knowledge and the object of knowledge is done.
Therefore, the vacuum heat insulation material of the application of the invention, can provide the equipment such as heat-shielding performance and the excellent refrigerator of energy-efficient performance.
In addition, if use to innermost layer the outsourcing material that formed by HDPE and sorbing material uses (5) and (8) of calcium oxide and appropriate hydrocarbon gas sorbing material A to compare, compared with (8) that then use glass wool core material with core material, the thermal conductivity of (5) of wet type copy paper core material is used to reduce.Thus, by using the wet type copy paper core material as the core material of the first mode of execution vacuum heat insulation material, heat-shielding performance can be improved further.
Disclosed mode of execution and embodiment are illustration above, and the present invention is not limited thereto.Scope of the present invention is not limited to the above-described embodiment and examples, but represents by claim, and comprises the content be equal to claim and all modifications carried out in right or distortion.
Industrial applicibility
Vacuum heat insulation material of the present invention can be applied to: the refrigerator used for heating various food, cooling, be incubated, cooler bin, HEATING BOX etc.; The dryer of dried object drying is made to dried object blowout hot blast; And the inside etc. of skin for the heat-shielding performance that improves building.

Claims (4)

1. a vacuum heat insulation material (1), is characterized in that comprising:
Outsourcing material (200);
Core material (100), is housed in the inside of described outsourcing material (200), is laminated by multiple nonwovens (110); And
Sorbing material (400), is housed in the inside of described outsourcing material (200),
Described nonwovens (110) at least comprises many inorfils utilizing continuous filament method to manufacture, in described nonwovens (110), most of inorfil in described many inorfils extends on the direction substantially parallel with the surface of described nonwovens (110)
Described outsourcing material (200) has thermofussion welding portion (300), makes to contact with each other between outsourcing material (200) to carry out thermofussion welding described thermofussion welding portion (300),
Described thermofussion welding portion (300) is formed by the material containing hydrocarbon,
Described sorbing material (400) by the carrying of the potassium permanganate of adsorbed hydrocarbons gas on porous substrate, described appropriate hydrocarbon gas after the inner pressure relief of the described outsourcing material (200) by containing described core material (100) thermofussion welding portion (300) described in thermofussion welding and seal described outsourcing material (200) time produce from described thermofussion welding portion, and to the diffusion inside of described outsourcing material
Near the described thermofussion welding portion carrying out thermofussion welding after described core material and described sorbing material are contained in described outsourcing material with decompression state, configure described sorbing material.
2. vacuum heat insulation material according to claim 1 (1), is characterized in that, the fiber diameter of described inorfil more than 3 μm, less than 15 μm, the average fiber length of described inorfil is at more than 3mm, below 15mm.
3. vacuum heat insulation material according to claim 1 (1), is characterized in that, described inorfil is glass fibre, and described sorbing material comprises the material of hygroscopic moisture.
4. an equipment (3,4,5,6), is characterized in that comprising:
Outer casing (301,411,421,501,601);
Internal box (302,412,422,503,603), is configured in the inner side of described outer casing (301,411,421,501,601); And
Vacuum heat insulation material (320,430,510,610), is configured between described outer casing (301,411,421,501,601) and described internal box (302,412,422,503,603),
Described vacuum heat insulation material (320,430,510,610) comprises vacuum heat insulation material according to claim 1 (1).
CN201080015047.5A 2009-04-07 2010-04-06 Vacuum insulation material and device provided with same Expired - Fee Related CN102388252B (en)

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