CN102362115A - Core material for vacuum insulation material, vacuum insulation material, and processes for producing these - Google Patents

Core material for vacuum insulation material, vacuum insulation material, and processes for producing these Download PDF

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Publication number
CN102362115A
CN102362115A CN201080013026XA CN201080013026A CN102362115A CN 102362115 A CN102362115 A CN 102362115A CN 201080013026X A CN201080013026X A CN 201080013026XA CN 201080013026 A CN201080013026 A CN 201080013026A CN 102362115 A CN102362115 A CN 102362115A
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China
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nonwovens
core material
heat insulation
vacuum heat
insulation material
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CN201080013026XA
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CN102362115B (en
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大堀进一
内田武
上野浩义
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Sharp Corp
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Sharp Corp
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L59/00—Thermal insulation in general
    • F16L59/06—Arrangements using an air layer or vacuum
    • F16L59/065—Arrangements using an air layer or vacuum using vacuum
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00—Insulation
    • F25D2201/10—Insulation with respect to heat
    • F25D2201/12—Insulation with respect to heat using an insulating packing material
    • F25D2201/124—Insulation with respect to heat using an insulating packing material of fibrous type
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D2201/00—Insulation
    • F25D2201/10—Insulation with respect to heat
    • F25D2201/14—Insulation with respect to heat using subatmospheric pressure

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  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Insulation (AREA)
  • Nonwoven Fabrics (AREA)
  • Paper (AREA)

Abstract

Provided is a core material for vacuum insulation materials which has excellent heat-insulating performance capable of surpassing a conventional heat-insulating performance limit and can be industrially mass-produced. Also provided are a vacuum insulation material equipped with the core material and processes for producing the core material and the vacuum insulation material. The core material (100) for vacuum insulation materials is one obtained by superposing a plurality of nonwoven fabrics (110). The nonwoven fabrics (110) contain at least a plurality of glass fibers (111, 112) produced by a continuous filament process. In the nonwoven fabrics (110), most glass fibers (111, 112) of the glass fibers extend in directions approximately parallel to the surfaces of the nonwoven fabrics (110). A binder ingredient is present in a relatively large amount in the surface layer parts of each nonwoven fabric (110) and is present in a relatively small amount in the inner part of each nonwoven fabric (110).

Description

Vacuum heat insulation material is with core material, vacuum heat insulation material and production method
Technical field
The present invention relates to vacuum heat insulation material with core material, vacuum heat insulation material and their production method.
Background technique
In the past, at the refrigerator that is used for various food are heated, cool off, are incubated and use, cooler bin, HEATING BOX etc., used thermal-protective material with various structures or performance.Because among thermal-protective material, the heat-shielding performance of vacuum heat insulation material is good, so vacuum heat insulation material is widely used in the heat insulation equipment such as household refrigerator of needs.Generally, seal outsourcing material, and make the inside of outsourcing material keep being in decompression state, thereby can obtain vacuum heat insulation material through after being filled into the inside of outsourcing material to the core material that constitutes by inorganic material.In inorganic material, the glass wool that adopts the glass fibre by flame method or centrifuge method manufacturing to constitute forms the core material of above-mentioned vacuum heat insulation material.
For example the open communique spy of Japan Patent to open the vacuum heat insulation material of 2005-265038 number (patent documentation 1) record be the glass wool that is made up of the glass fibre as inorfil to be carried out wet type manufacture paper with pulp; And with many range upon range of then uses of the inorfil thin slice that obtains as core material; Particle diameter in the inorfil contains ratio below 0.1 quality % at the particle more than the 30 μ m; Average fibre diameter in the inorfil is 0.2～6 μ m, and inorfil is arranged with respect to the sheet surface along continuous straight runs.
In addition; The vacuum heat insulation material that the open communique spy of Japan Patent opens 2006-17169 number (patent documentation 2) record constitutes glass wool by the glass fibre as the inorfil stacking material; Core material is made up of this glass wool; Inner at outsourcing material the core material reduced pressure sealing, the density of the core material in the vacuum heat insulation material is 200～270kg/m 3, the core material of opening behind the outsourcing material includes the glass fibre of length of staple more than 100 μ m more than 75%.
Patent documentation 1: Japan Patent open communique spy open 2005-265038 number
Patent documentation 2: Japan Patent open communique spy open 2006-17169 number
Summary of the invention
Fig. 8 schematically shows in the past in the glass wool that core material adopted as vacuum heat insulation material the planimetric map of the distribution of glass fibre.Fig. 9 is plane electronics photomicrograph (100 times of a magnification factor); Its expression is in the past in the glass wool that core material adopted as vacuum heat insulation material; Distribution before glass fibre is compressed, Figure 10 is the section electron micrograph (100 times of magnification factors) of expression same distribution state.
As shown in Figure 8, can find out that in glass wool 500 many glass fibres 510 of various length of staple extend and random distribution to all directions.In addition, like Fig. 8, shown in Figure 9, in the glass wool that utilizes flame method or centrifuge method to make, sneaked into length of staple at short fibre below the 1mm and the microfibre of fiber diameter below 1 μ m with respect to main fibre.Above-mentioned short fibre or microfibre are filled between the main fibre or interweave between main fibre, between fiber, produce transmission of heat, can think that institute is so that the heat-shielding performance reduction owing to cause transmission of heat along the core material thickness direction.In addition, can find out that in above-mentioned glass wool, main fibre also includes the fiber of a large amount of bendings or distortion.
Owing to constitute glass wool in the above described manner; So as the open communique spy of Japan Patent opens 2005-265038 number (patent documentation 1) record, when utilizing wet type to manufacture paper with pulp to form thin slice; Even want to make glass fibre to arrange in the horizontal direction, also be difficult to arrange most glass fibre with respect to sheet surface.
In addition, as the open communique spy of Japan Patent opens 2006-17169 number (patent documentation 2) record,, make the core material density of the glass fibre of length of staple more than 100 μ m that includes more than 75% reach 200～270kg/m even push glass wool 3, also be difficult to arrange most glass fibre.
Therefore, the core material of the vacuum heat insulation material of above-mentioned communique record all is difficult to prevent because of producing the heat-shielding performance reduction that transmission of heat causes between the fiber.And the thermal conductivity of the vacuum heat insulation material that obtains is limited so utilization improvement way in the past improves the heat-shielding performance of vacuum heat insulation material about 2mW/mK.
The object of the present invention is to provide vacuum heat insulation material with core material, have this vacuum heat insulation material with the vacuum heat insulation material of core material and their production method; Said vacuum heat insulation material has good heat-shielding performance and can industrial mass production with core material, and this good heat-shielding performance can surmount any improvement of in the past the thermal insulation the subject of knowledge and the object of knowledge being done.
Inventor of the present invention is in order to solve the problem of the core material existence that vacuum heat insulation material adopted in the past; Carried out wholwe-hearted research repeatedly; Its result finds: through making in constituting the fiber of vacuum heat insulation material with core material, include at least and utilize many inorfils of continuous filament method manufacturing just can realize above-mentioned purpose.Wherein, so-called continuous filament method is a kind of fibre manufacture, through making molten glass flow through lining nozzle, and continuously outflow, stretching, Fibrotic operation, generates continuous fiber.Based on above-mentioned discovery, vacuum heat insulation material of the present invention has following characteristic with core material.
Vacuum heat insulation material of the present invention with core material by many range upon range of the forming of nonwovens.Nonwovens comprises many inorfils that utilize continuous filament method to make at least.In nonwovens, the most of inorfil in many inorfils with the surperficial substantially parallel direction of nonwovens on extend.
Adopt continuous filament method many very little fibers of producd fibers diameter difference in a large number.In addition, utilize each fiber straightness accuracy of the inorfil that continuous filament method makes very high.Therefore, through cutting into certain substantially length to many inorfils that utilize the continuous filament method manufacturing, can under the very high state of straightness accuracy, obtain many inorfils that fiber diameter difference is very little and length is identical substantially.
At least include many inorfils that utilize continuous filament method to make owing to constitute the nonwovens of core material of the present invention; So when using above-mentioned many inorfils to form nonwovens; If be arranged in each inorfil on the surperficial parallel direction with respect to nonwovens; Can easily arrange many inorfils so that most inorfil with the surperficial substantially parallel direction of nonwovens on extend.At this moment, though the major part of many inorfils with the substantially parallel direction in the surface of nonwovens on extend, be not to be closely arranged in each other on the parallel direction, but in the plane that forms nonwoven surface towards the random direction dispersed arrangement.Therefore, can reduce the inorfil that is filled between many inorfils that constitute core material as far as possible, and can reduce the inorfil that interweaves between many inorfils as far as possible, so can prevent between inorfil, to produce transmission of heat.Thus; Through preventing to produce transmission of heat along the core material thickness direction; The thermal conductivity of core material is reduced, and the vacuum heat insulation material that obtains has good heat-shielding performance with core material, and this good heat-shielding performance can surmount any improvement of in the past the thermal insulation the subject of knowledge and the object of knowledge being done.
The vacuum heat insulation material of said structure with the nonwovens that core material adopted, for example be made up of glass fibre in, do not have the combination force between the fiber.Therefore, in order to prevent that in the manufacturing process of nonwovens glass fibre from coming off, and, in machine hand's preface, need to use tackiness agent in order to prevent that in the manufacturing procedure of subsequent handling shape is at random.
Liquid tackiness agent concentrates on around the crossover sites of many glass fibres because of surface tension easily.Therefore, even be in a contact condition between the adjacent glass fibre, also there is this contact position of adhesive coverage possibility on every side.Can expect thus to produce transmission of heat, so can think that liquid tackiness agent is not preferred through tackiness agent.Therefore, consider to use granular or fibrous tackiness agent.
Make tackiness agent at use granular tackiness agent or fibre adhesive; And these tackiness agent dispersing and mixing in fiberglas chopped strand; Utilize wet type to copy under the situation of paper manufactured nonwovens; Can think that most tackiness agent is positioned at beyond the point of contact of fiber, and overlap between fiber by tackiness agent.Be envisioned that above-mentioned overlap joint is extremely very thin, it is very little to produce heat conducting possibility.But, in order to bring up to ultimate state to heat-shielding performance, the transmission of heat that needs inhibition to cause because of above-mentioned tackiness agent.
Therefore; For the small transmission of heat that prevents to cause because of the tackiness agent that rides between the fiber, bring up to ultimate state to heat-shielding performance, can consider before vacuum seal; Remove or reduce the tackiness agent in the core material through the method for utilizing thermolysis, come further to improve heat-shielding performance.
Promptly; Can consider before being sealing into outsourcing material inside to core material; Through high at the heat decomposition temperature of specific viscosity mixture and liken under the low-melting temperature for the employed glass fibre of one of inorfil and handle, utilize thermolysis only binder removal.In addition, for example using under the polyvinyl alcohol situation of water-soluble resin tackiness agent such as (PVA), except said method, can consider to utilize warm water etc. to clean to remove or reduce tackiness agent as tackiness agent.
But; Remove the tackiness agent in the core material in order to utilize said method; Not only need long heating process or washing process, and the intensity of the core material behind the removal tackiness agent is very low, also needs the time so core material is sealing into the inner operation of outsourcing material.Therefore, although obtain the extraordinary vacuum heat insulation material of heat-shielding performance, cause being difficult to utilize the manufacturing equipment of vacuum heat insulation material in the past to carry out the new problem of industrial mass production.
Inventor of the present invention is in order to address the above problem; Carried out wholwe-hearted research repeatedly; Its result finds: vacuum heat insulation material with core material in, make in constituting the fiber of vacuum heat insulation material with core material, include many fibers that utilize the continuous filament method manufacturing at least; Through using the minute quantity fluid binder, can solve above-mentioned new problem as tackiness agent.Wherein, so-called fluid binder is to instigate adhesive ingredients dissolving and become liquid state or make the adhesive ingredients emulsionization and become liquid state.
Under the situation of using granular or fibre adhesive; For the transmission of heat that suppresses to cause, if reduce to ultimate state to the adhesive ingredients content in the nonwovens, then because adhesive ingredients evenly distribution in nonwovens because of adhesive ingredients; So not only intensity reduces; And fiber comes off from the surface of nonwovens easily, the fiber that in making the nonwovens operation, comes off in a large number attached to drying equipment in, produce and bad phenomenon such as be difficult to produce continuously.
On the other hand; Inventor of the present invention finds: under the situation of using fluid binder; Even the content of the adhesive ingredients in the nonwovens is considerably less; Compare with the situation of having used granular or fibre adhesive, also not only can obtain sufficient intensity required in producing continuously, and heat-shielding performance is good.Its reason is inferred as follows:
Because in the heat drying operation of fluid binder when making nonwovens; When the inner water evaporation of the netted thing of nonwovens; Tackiness agent also moves together, so tackiness agent concentrates on two surfaces of nonwovens, produces the tendency that the inner tackiness agent of nonwovens tails off.
In addition, fluid binder causes around the crossover sites that concentrates on many fibers easily because of surface tension.Though this situation sees not to be preferred from reducing heat conducting angle, sees it is preferred from the angle that improves intensity.Therefore; Use the situation of fluid binder to compare with the situation of using granular or fibre adhesive; Even the content of the adhesive ingredients in the nonwovens is considerably less; Can make combination more securely between the fiber owing to concentrate on two lip-deep tackiness agents of nonwovens,, also can obtain making the nonwovens operation and making needed intensity in the vacuum insulation material material process so improved integral intensity.
In addition because inner at nonwovens, the content of adhesive ingredients than the surface of nonwovens still less, so the transmission of heat of carrying out through tackiness agent is considerably less.
For these reasons; Under the situation of using the minute quantity fluid binder; Owing to can make between near the fiber the nonwoven surface bonding each other effectively; Can satisfy the desired enough intensity of industrial mass production so vacuum heat insulation material of the present invention has with core material, on the other hand, can make the amount of the inner tackiness agent of nonwovens considerably less.
In addition, under the situation of using granular or fibre adhesive, the phenomenon that tackiness agent moves in the heat drying operation as fluid binder can take place hardly in nonwovens.
Based on inventor's above discovery, vacuum heat insulation material of the present invention has following characteristic with core material.
Vacuum heat insulation material of the present invention with core material by many range upon range of the forming of nonwovens.Nonwovens comprises many inorfils that utilize continuous filament method to make at least.In nonwovens, the most of inorfil in many inorfils extends on the direction substantially parallel with nonwoven surface.The vacuum heat insulation material with said structure with core material in, in the skin section of nonwovens, have the adhesive ingredients of relative volume, have the adhesive ingredients of relatively small amount in the inside of nonwovens.
Vacuum heat insulation material of the present invention with core material in, preferably: the content of adhesive ingredients with respect to nonwovens more than the 0.1 quality %, below the 1.5 quality %.
If adhesive ingredients content is less than 0.1 quality %, then owing to making the nonwovens operation and making strength deficiency in the vacuum insulation material material process, produce the phenomenon that fiber comes off or disperses from nonwoven surface in a large number, so be difficult to industrial mass production.In addition, if adhesive ingredients content surpasses 1.5 quality %, then compare with the situation of using granular or fibre adhesive, vacuum heat insulation material uses the core material heat-shielding performance to be equal extent or following, can not obtain using the effect of fluid binder.
Vacuum heat insulation material of the present invention with core material in, preferably: the fiber diameter of inorfil is more than the 3 μ m, below the 15 μ m, and the average fiber length of inorfil is more than the 3mm, below the 15mm.In this case, can reduce the thermal conductivity of core material to greatest extent, thereby the vacuum heat insulation material that can obtain having the most excellent heat-shielding performance is used core material.
Vacuum heat insulation material of the present invention with core material in, preferably: inorfil is a glass fibre.In this case, because other inorfils of thermal conductivity ratio of glass fibre are little, for example little than ceramic fiber, so, can further improve the heat-shielding performance of core material through reducing the thermal conductivity of material self.
Vacuum heat insulation material of the present invention comprises the core material that outsourcing material is inner with being housed in outsourcing material.The inside of outsourcing material can keep being in decompression state.Core material comprises that at least a vacuum heat insulation material with above-mentioned any one characteristic uses core material.
Vacuum heat insulation material of the present invention comprises the steps: to use at least many inorfils and fluid binder, utilizes wet type to copy the step that the paper method is made nonwovens with the production method of core material; Above-mentioned many inorfils utilize the continuous filament method manufacturing; In said step, the most of inorfil in many inorfils is extended on the direction substantially parallel with the nonwoven surface of making; And many nonwovens are carried out range upon range of step.
In the production method of vacuum heat insulation material of the present invention with core material, use many inorfils and fluid binder at least, above-mentioned many inorfils utilize continuous filament method manufacturing.When using above-mentioned many inorfils to utilize wet type to copy the paper method when making nonwovens; If each inorfil is arranged on the surperficial parallel direction with respect to nonwovens; Then can easily make and arrange many inorfils, so that most inorfil extends on the direction substantially parallel with nonwoven surface.
At this moment, the major part of many inorfils with the surperficial substantially parallel direction of nonwovens on extend, but be not closely to be arranged on the parallel direction each other, but in the plane that forms nonwoven surface towards the random direction dispersed arrangement.Thus; Even range upon range of many nonwovens in order to constitute core material; Owing to can reduce the inorfil that is filled between many inorfils as far as possible; And can reduce the inorfil that interweaves between many inorfils as far as possible, produce transmission of heat so can prevent to be arranged between the inorfil on the substantially parallel direction with nonwoven surface.
In addition, in the drying process when making nonwovens, move to the surface of nonwovens when following inner water of nonwovens or solvent evaporation, fluid binder concentrates in two top layers of nonwovens.Therefore; Even the amount of the tackiness agent that contains in the nonwovens is few; Also can improve the intensity of nonwoven surface,, not only can obtain making the nonwovens operation and making needed intensity in the vacuum insulation material material process so the fiber that can suppress on the nonwoven surface disperses; And owing to the inner binder content of nonwovens further reduces, so the transmission of heat of carrying out through tackiness agent also becomes considerably less.
Therefore; Through prevent to produce transmission of heat as far as possible along the core material thickness direction; The thermal conductivity of core material is reduced; Thereby the vacuum heat insulation material that can obtain having excellent adiabatic capacity is used core material, and this good heat-shielding performance can surmount any improvement of in the past the thermal insulation the subject of knowledge and the object of knowledge being done.
In addition; Because even the amount of the tackiness agent that contains in the nonwovens is few; Also have and making the nonwovens operation and making needed intensity in the vacuum insulation material material process; And the fiber that disperses or come off from nonwoven surface is few, so can obtain using core material as the vacuum heat insulation material of medium material that can the industrial mass production vacuum heat insulation material.
The production method of vacuum heat insulation material of the present invention comprises the steps: to use at least many inorfils and fluid binder, utilizes wet type to copy the step that the paper method is made nonwovens; Above-mentioned many inorfils utilize the continuous filament method manufacturing; In said step, the most of inorfil in many inorfils is extended on the direction substantially parallel with the nonwoven surface of making; Many nonwovens are carried out range upon range of step; And many nonwovens after range upon range of are housed in the inside of outsourcing material and make the inside of outsourcing material keep being in the step of decompression state.
In the production method of vacuum heat insulation material of the present invention, use many inorfils and fluid binder at least, above-mentioned many inorfils utilize the continuous filament method manufacturing.When using above-mentioned many inorfils to utilize wet type to copy the paper method when making nonwovens; If be arranged in each inorfil on the surperficial parallel direction with nonwovens; Then can easily arrange many inorfils so that most inorfil with the surperficial substantially parallel direction of nonwovens on extend.At this moment, though the major part of many inorfils with the surperficial substantially parallel direction of nonwovens on extend, be not closely to be arranged on the parallel direction each other, but in the plane that forms nonwoven surface towards the random direction dispersed arrangement.Therefore; Even range upon range of many nonwovens in order to constitute core material; Owing to can reduce the inorfil that is filled between many inorfils as far as possible; And can reduce the inorfil that interweaves between many inorfils, so also can prevent between inorfil, to produce transmission of heat as far as possible.Through being housed in the inside of outsourcing material to many nonwovens after range upon range of, and make the inside of outsourcing material keep being in decompression state, can make vacuum heat insulation material.
In addition, because the content of the adhesive ingredients of nonwovens inside is considerably less, so adhesive ingredients is also very low attached to the probability on the crossover sites of many inorfils.Therefore, the transmission of heat of carrying out through tackiness agent is few.
Like this, can prevent to produce transmission of heat along the core material thickness direction.Therefore, the thermal conductivity of core material is reduced.Thus, can obtain having the vacuum heat insulation material of excellent adiabatic capacity, this good heat-shielding performance can surmount any improvement of in the past the thermal insulation the subject of knowledge and the object of knowledge being done.
In addition, a spot of tackiness agent makes between the fiber of nonwoven surface bonding each other effectively.Therefore, can guarantee nonwovens needed intensity in making nonwovens operation and manufacturing vacuum insulation material material process.Thus, can the industrial mass production vacuum heat insulation material.
As stated; According to the present invention; Through using many inorfils and the fluid binder utilize that continuous filament method makes at least; The thermal conductivity of core material is reduced, thus the vacuum heat insulation material that can obtain having excellent adiabatic capacity with core material and vacuum heat insulation material with this core material, said good heat-shielding performance can surmount in the past any improvement to thermal insulation the subject of knowledge and the object of knowledge work.
In addition; According to the present invention,, there is the adhesive ingredients of relatively small amount in the inside of nonwovens owing in the skin section of nonwovens, there is the adhesive ingredients of relative volume; So tackiness agent can make the fiber on two surfaces of nonwovens bonding each other separately effectively; Not only can make the transmission of heat that causes because of tackiness agent considerably less, can also guarantee that nonwovens is making the nonwovens operation and making needed intensity in the vacuum insulation material material process, so can the industrial mass production vacuum heat insulation material.
Description of drawings
Fig. 1 is the sectional view that schematically illustrates one embodiment of the present invention, (A) configuration of expression core material and outsourcing material, and (B) after the inner pressure relief of expression outsourcing material, the state that vacuum heat insulation material is inner.
Fig. 2 is the stereogram that schematically illustrates one embodiment of the present invention, (A) configuration of expression core material and outsourcing material, and (B) after the inner pressure relief of expression outsourcing material, the state that vacuum heat insulation material is inner.
Fig. 3 is the planimetric map of one embodiment of the present invention, schematically illustrates the distribution of the glass fibre of the nonwovens that core material adopted that constitutes vacuum heat insulation material.
Fig. 4 is the plane electronics photomicrograph (100 times of magnification factors) of expression one embodiment of the present invention, and the glass fibre that expression constitutes the nonwovens that core material adopted of vacuum heat insulation material is compressed preceding distribution.
Fig. 5 is the section electron micrograph (100 times of magnification factors) of expression one embodiment of the present invention, and the glass fibre that expression constitutes the nonwovens that core material adopted of vacuum heat insulation material is compressed preceding distribution.
Fig. 6 is the sectional view of a kind of manner of comparison of the present invention, schematically illustrates in the nonwovens that core material adopted of vacuum heat insulation material granular or the distribution of fibrous tackiness agent on the nonwoven thickness direction.
Fig. 7 is the sectional view of one embodiment of the present invention, schematically illustrates in the nonwovens that core material adopted of vacuum heat insulation material the distribution of fluid binder on the nonwoven thickness direction.
Fig. 8 schematically illustrates in the past in the glass wool that core material adopted as vacuum heat insulation material the plan view of the distribution of glass fibre.
Fig. 9 is plane electronics photomicrograph (100 times of a magnification factor), and expression is in the past in the glass wool that core material adopted as vacuum heat insulation material, the distribution before glass fibre is compressed.
Figure 10 is section electron micrograph (100 times of a magnification factor), and expression is in the past in the glass wool that core material adopted as vacuum heat insulation material, the distribution before glass fibre is compressed.
Description of reference numerals
1 vacuum heat insulation material
100 core materials
200 outsourcing materials
110 nonwovens
111,112 glass fibres.
Embodiment
According to accompanying drawing mode of execution of the present invention is described below.
Fig. 1 is the sectional view that schematically illustrates the vacuum heat insulation material structure of one embodiment of the present invention.State before (A) expression outsourcing material inner pressure relief of Fig. 1, the state after (B) expression outsourcing material inner pressure relief of Fig. 1.
As shown in Figure 1, in vacuum heat insulation material 1, core material 100 is housed in the inside of outsourcing material 200, and said outsourcing material 200 has barrier properties for gases and forms a bag shape.
Shown in Fig. 1 (A), core material 100 is cascaded by many nonwovens 110.Each layer nonwovens 110 uses glass fibre and a spot of tackiness agent of one of inorfil, and utilization is copied the paper method and processed.
Shown in Fig. 1 (B), after the inner pressure relief of outsourcing material 200, utilize the external pressure of outsourcing material 200 that core material 100 is compressed, many nonwovens 110 that constitute core material 100 are extruded and contact.Under the state after the inner pressure relief of outsourcing material 200, the density of core material 100 is at 100～400kg/m 3Scope in.
Constitute nonwovens in the above described manner, and constitute core material nonwovens is range upon range of, be configured in the inside of outsourcing material to core material again and reduce pressure, constitute vacuum heat insulation material.
Fig. 2 is the stereogram that schematically illustrates one embodiment of the present invention, (A) configuration of expression core material and outsourcing material, and (B) after the inner pressure relief of expression outsourcing material, the state that vacuum heat insulation material is inner.A part of only having represented each nonwovens, core material, outsourcing material respectively.
Shown in Fig. 2 (A), range upon range of many nonwovens 110, form core material 100.Core material 100 is covered by outsourcing material 200.Outsourcing material 200 has barrier properties for gases and forms a bag shape, covers whole core material 100.
Shown in Fig. 2 (B), if reduced pressure in the inside of the outsourcing material 200 of bag shape, then core material 100 is compressed.If core material 100 is compressed, many nonwovens 110 mutual extrusion and contacting then.
Inventor of the present invention is for the heat-shielding performance of the vacuum heat insulation material 1 that improves said structure; Carried out wholwe-hearted research; Its result finds through using the nonwovens 110 that is made up of inorfil with specified conditions and tackiness agent as core material 100; Significantly improve the heat-shielding performance of vacuum heat insulation material 1, thereby realized the present invention.
Therefore, as shown in Figure 1, nonwovens of the present invention 110 constitutes the core material 100 that vacuum heat insulation materials 1 are adopted, and includes many inorfils and the fluid binder that utilizes that continuous filament method makes at least.
In addition; As shown in Figure 1; Vacuum heat insulation material 1 of the present invention comprises outsourcing material 200 and the core material 100 that is housed in outsourcing material 200 inside, and outsourcing material 200 can keep its inside to be in decompression state, constitutes core material 100 through range upon range of nonwovens 110.Nonwovens 110 includes many inorfils and fluid binder at least, and above-mentioned many inorfils utilize the continuous filament method manufacturing.
Inorfil can give an example glass fibre, ceramic fiber, rock wool fibers etc.; In order to constitute core material of the present invention; Need the thin fiber of diameter; So that can be with the angle consideration of lower price circulation and from the little angle consideration of the thermal conductivity of raw material itself, inorfil preferably uses glass fibre from producing the thin fiber of said diameter in a large number.
In one embodiment of the invention, use cut into certain-length glass fibre, utilize nonwovens 110 that wet type copies the paper manufactured to use as the core material 100 of vacuum heat insulation material.Wherein, The glass fibre that what is called cuts into certain-length is meant: utilize continuous filament method to pull out molten glass and be shaped from a plurality of nozzles; Tie together the glass fibre as thread continuous fiber of the even thickness after hundreds of～thousands of shapings and be wound in precursor, utilize guillotine cutting machine etc. to cut into specific length to this precursor.Call fiberglas chopped strand to the precursor that cuts into the glass fibre after the specific length like this.
Because the glass fibre that obtains like this is to cut into specific length to continuous fiber with certain size,, and have uniform fibers diameter and the section that is roughly circle substantially so this glass fibre is straightness accuracy height and the big fiber of rigidity.That is, adopt continuous filament method many very little fibers of producd fibers diameter difference in a large number.In addition, utilize each fiber straightness accuracy of the inorfil that continuous filament method makes very high.Therefore, through cutting into certain substantially length to many inorfils that utilize the continuous filament method manufacturing, can under the very high state of straightness accuracy, obtain many inorfils that fiber diameter difference is very little and length is identical substantially.
Thus; Using this glass fibre to utilize wet type to copy under the situation of paper manufactured nonwovens 110; Can obtain following nonwovens 110: promptly; Though fiber extends fiber orientation random direction dispersed arrangement in the plane that forms nonwovens 110 surfaces on the direction parallel with the surface cardinal principle of nonwovens 110.
Fig. 3 is the planimetric map of one embodiment of the present invention, schematically illustrates the distribution of the glass fibre of the nonwovens that core material adopted that constitutes vacuum heat insulation material.Fig. 3 is the nonwovens that expression is made up of the layer glass layer of fibers.Fig. 4 is the plane electronics photomicrograph (100 times of magnification factors) of expression one embodiment of the present invention; Distribution before the glass fibre of the nonwovens that core material adopted of expression vacuum heat insulation material is compressed, Fig. 5 is the section electron micrograph (100 times of magnification factors) of expression same distribution state.
As shown in Figure 3; Many the glass fibres 111 that form the upper strata extend on the direction parallel with the surface cardinal principle of nonwovens 110 with many glass fibres 112 that form lower floor; But be not closely to be arranged on the parallel direction each other, but dispersed arrangement become towards random direction in the plane that forms nonwovens 110 surfaces.In addition, like Fig. 4, shown in Figure 5, can find out that the straightness accuracy of each fiber is very high.And, though most fiber with the substantially parallel direction in the surface of nonwovens 110 on extend, in the plane that forms nonwovens 110 surfaces towards the random direction dispersed arrangement.
As stated; At least include many glass fibres 111,112 that utilize continuous filament method to make owing to constitute the nonwovens 110 of core material 100 of the present invention as one of inorfil; So when using above-mentioned many glass fibres 111,112 to form nonwovens 110; If each glass fibre 111,112 is arranged on the surperficial parallel direction with respect to nonwovens 110; Then can easily arrange many glass fibres 111,112, so that most glass fibre 111,112 extends on the direction parallel with the surface cardinal principle of nonwovens 110.At this moment; Though the major part of many glass fibres 111,112 is extended on the direction parallel with the surface cardinal principle of nonwovens 110; But be not closely to be arranged on the parallel direction each other, but in the plane that forms nonwovens 110 surfaces towards the random direction dispersed arrangement.Be filled in many glass fibres 111 that constitute core material 100, the glass fibre between 112 owing to can reduce as far as possible; And can reduce as far as possible and interweave, so can prevent at glass fibre 111, produce transmission of heat between 112 at many glass fibres 111, glass fibre between 112.Therefore; Through preventing to produce transmission of heat along core material 100 thickness directions; The thermal conductivity of core material 100 is reduced; Thereby the vacuum heat insulation material that can obtain having excellent adiabatic capacity is with core material 100 and vacuum heat insulation material 1 with this core material 100, and said good heat-shielding performance can surmount any improvement of in the past the thermal insulation the subject of knowledge and the object of knowledge being done.
Be not particularly limited the composition of glass fibre 111,112, can adopt C glass, D glass, E glass etc., but calm facile angle sets out, preferably adopt E glass (aluminium borosilicate glass).
As stated; Core material of the present invention is processed by nonwovens 110; The inorfil that forms this nonwovens 110 is to cut off the glass fibre with specific length 111,112 form to continuous fiber with given size, and above-mentioned glass fibre 111,112 straightness accuracys are very high and have and be roughly circular section.Therefore, many glass fibres 111,112 that disperse towards random direction are not limited to be arranged in parallel side by side, are the some contact owing to each bar glass fibre 111, between 112, so can significantly suppress glass fibre 111, the transmission of heat between 112.
Though also can consider to adopt other raw material to come instead of glass fiber 111,112; But generally use the inorganic fibers such as alumina fibre chopped strand of alumina fibre more expensive than glass fibre 111,112; And thermal conductivity is high, so be not preferable 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 cross fibers because of external pressure, causes face contact or the minimizing of vacuum space ratio between the fiber.Its result, core material uses the vacuum heat insulation material of organic fiber because thermal conductivity is high, so be not preferable material.
In the nonwovens 110 that constitutes by glass fibre 111,112 that vacuum heat insulation material of the present invention is adopted with core material 100, there is not the combination force between the fiber.Therefore, come off, and, in machine hand's preface, need to use tackiness agent in order to prevent that in the manufacturing procedure of subsequent handling shape is at random in order in the manufacturing process of nonwovens 110, to prevent glass fibre 111,112.Yet, because nonwovens 110 will be wrapped in inside by outsourcing material 200 as the core material 100 of vacuum heat insulation material 1, so need be restricted to bottom line to the use amount of tackiness agent.
Based on inventor's following discovery, the tackiness agent among the present invention does not use granular or fibrous tackiness agent, and uses fluid binder.
Inventor of the present invention finds: under the situation of using fluid binder; Even the content of the adhesive ingredients in the nonwovens 110 is considerably less; Compare with the situation of using granular or fibre adhesive; Also not only can obtain enough intensity required in producing continuously, and heat-shielding performance is good.Its reason is inferred as follows:
Because in the heat drying operation of fluid binder when making nonwovens 110; When the inner water evaporation of nonwovens 110 reticulated works; Tackiness agent also moves together, so tackiness agent concentrates on two surfaces of nonwovens 110, produces the tendency that nonwovens 110 inner tackiness agents tail off.
In addition, fluid binder concentrates on around the crossover sites of many glass fibres 111,112 because of surface tension easily.Though this situation sees not to be preferred from reducing heat conducting angle, sees it is preferred from the angle that improves intensity.Therefore; Use the situation of fluid binder to compare with the situation of using granular or fibre adhesive; Even the content of the adhesive ingredients in the nonwovens 110 is considerably less; Also can make glass fibre 111, combine more securely between 112 owing to concentrate on 110 two lip-deep tackiness agents of nonwovens,, can obtain needed intensity in the manufacturing process of the manufacturing process of nonwovens 110 and vacuum heat insulation material 1 so improved bulk strength.
In addition because in nonwovens 110 inside, the content of adhesive ingredients than the surface of nonwovens 110 still less, so the transmission of heat of carrying out through tackiness agent is considerably less.
For these reasons; Under the situation of using the minute quantity fluid binder; Because can make the glass fibre 111 of nonwovens 110 near surfaces effectively, bonding each other between 112; So vacuum heat insulation material of the present invention has the desired enough intensity of industrial mass production with core material 100, on the other hand, can make the amount of the inner tackiness agent of nonwovens 110 considerably less.
Fig. 6 is the sectional view of a kind of manner of comparison of the present invention, schematically illustrates in the nonwovens that core material adopted of vacuum heat insulation material granular or the distribution of fibrous tackiness agent on the nonwoven thickness direction.Fig. 7 is the sectional view of one embodiment of the present invention, schematically illustrates in the nonwovens that core material adopted of vacuum heat insulation material the distribution of fluid binder on the thickness direction of nonwovens.In addition, in Fig. 6, the part shown in the point is represented the distribution of tackiness agent.In Fig. 7, the distribution of the deep or light expression tackiness agent of black.
As shown in Figure 6, under the situation of using granular or fibre adhesive, the adhesive ingredients that is expressed as point-like evenly disperses on the thickness direction of nonwovens.In contrast, as shown in Figure 7, used in the present invention under the situation of fluid binder, on the thickness direction of nonwovens, the adhesive ingredients of volume is present in the skin section of nonwovens relatively, and the adhesive ingredients of relatively small amount is present in the inside of nonwovens.The content of fluid binder is with respect to nonwovens preferably in the scope more than 0.1 quality %, below the 1.5 quality %.
In addition, though fluid binder also can use inorganic bond, if use inorganic bond; Then the crooked pliability of fiber assembly is relatively poor, that is, the crooked pliability of nonwovens is relatively poor; In addition; Under situation about using as product, owing to use the cost of inorganic bond higher than the cost that uses organic bond, so preferably use organic bond.
Fluid binder of the present invention is: acrylic resin, epoxy resin, phenolic resin, styrene resin; Or the emulsion of polyethylene, polypropylene, polyester resin etc.; Or be dissolved in the solution in the solvent to them; Or the aqueous solution of water-soluble binders such as polyvinyl alcohol (PVA), starch etc., though, consider, be fit to use emulsion acrylic resin or polyvinyl alcohol water solution etc. from the relation of intensity and cost so long as liquid state does not just have special qualification.
In a kind of mode of execution of vacuum heat insulation material of the present invention with the production method of core material 100; At first; At least use many glass fibre 111,112 and fluid binders as one of inorfil, utilize wet type to copy the paper method to make nonwovens 110, above-mentioned many glass fibres 111,112 utilize the continuous filament method manufacturing.Thus, the most of glass fibre 111,112 in many glass fibres is extended on the direction parallel with the surface cardinal principle of the nonwovens of making 110.Then, range upon range of many nonwovens 110.
In addition; In a kind of mode of execution of the production method of vacuum heat insulation material 1 of the present invention; At first, use many glass fibres 111,112 and fluid binder at least, utilize wet type to copy the paper method to make nonwovens 110, above-mentioned many glass fibres 111,112 utilize the continuous filament method manufacturing.Thus, the most of glass fibre 111,112 in many glass fibres is extended on the direction parallel with the surface cardinal principle of the nonwovens of making 110.Then, range upon range of multi-layer nonwoven fabrics 110.After this, be housed in the inside of outsourcing material 200 to many nonwovens 110 after range upon range of, make that outsourcing material 200 is inner to keep being in decompression state.
In addition; In a kind of mode of execution of vacuum heat insulation material of the present invention with the production method of core material 100 or vacuum heat insulation material 1; Preferably use fluid binders such as the emulsion of above-mentioned resin, above-mentioned resin aqueous solution; And preferably adopt following method: first-class with the vaporific glass fibre 111,112 that is sprayed on through sprayer etc. this fluid binder, make fluid binder attached on the glass fibre 111,112.
In a kind of mode of execution of the production method of vacuum heat insulation material of the present invention, use many glass fibres 111,112 and fluid binder at least, above-mentioned many glass fibres 111,112 utilize the continuous filament method manufacturing.When using above-mentioned many glass fibres 111,112 to utilize wet type to copy the paper method when making nonwovens 110; If each glass fibre is arranged on the surperficial parallel direction with respect to nonwovens 110; Then can easily arrange many glass fibres so that most glass fibre 111,112 with the surperficial substantially parallel direction of nonwovens 110 on extend.At this moment; Though the major part of many glass fibres 111,112 with the surperficial substantially parallel direction of nonwovens 110 on extend; But be not closely to be arranged on the parallel direction each other, but in the plane that forms nonwovens 110 surfaces towards the random direction dispersed arrangement.Therefore; Even range upon range of many nonwovens 110 in order to constitute core material 100; Owing to can reduce the glass fibre that is filled between many glass fibres as far as possible; And can reduce the glass fibre that interweaves between many glass fibres, so also can prevent between glass fibre, to produce transmission of heat as far as possible.In addition, through being housed in the inside of outsourcing material 200 to range upon range of many nonwovens 110, and make the inside of outsourcing material 200 keep being in decompression state, can make vacuum heat insulation material 1.Thus; Through preventing to produce transmission of heat along core material 100 thickness directions; The thermal conductivity of core material 100 is reduced; Thereby can obtain having the core material 100 and the vacuum heat insulation material 1 with this core material 100 of excellent adiabatic capacity, said good heat-shielding performance can surmount any improvement of in the past the thermal insulation the subject of knowledge and the object of knowledge being done.
Utilize wet type to copy the paper manufactured nonwovens 110 that constitutes by glass fibre 111,112 used in the present invention.Copy in the paper method in wet type,, make with certain-length and cut off the fiberglas chopped strand monofilamentization that glass fibre forms, and decentralized configuration becomes stratiform, can obtain the nonwovens 110 that constitutes by stranded less glass fibre 111,112 through adding suitable dispersing agent.Therefore, the quantity of parallel glass fibre 111,112 side by side is considerably less, and most glass fibre 111,112 is the some contact between adjacent fiber.Like this, on thickness direction, have high compression-strength and the low-down nonwovens 110 of thermal conductivity owing to can produce, so above-mentioned nonwovens 110 is suitable as the core material 100 of vacuum heat insulation material 1 very much.
In production method of the present invention, adopt wet type to copy the paper method nonwovens 110 is manufactured paper with pulp, this is manufactured paper with pulp can use fourdrinier paper machine, short net paper making machine, tiltedly net known paper making machine such as formula paper making machine.
Usually, the nonwovens that is made up of glass fibre is used as thermal-protective material or the electrical insulator that has stable on heating thermal-protective material, has refractory nature.Therefore, because need having, nonwovens can bear the intensity of pulling open or puncturing etc., so need be interweaved mostly between the fiber.The nonwovens that is made up of the glass fibre that is used for such use utilizes mostly to be copied the paper manufactured and forms, and this is copied the paper method and uses fourdrinier paper machine, short net paper making machine.
And the nonwovens 110 that is made up of glass fibre 111,112 used in the present invention is housed in the inside of outsourcing material 200 as core material 100, so not too require the intensity of cloth.In addition, owing to make the consistent paper method of copying of fiber direction that the area of contact between the fiber is increased easily, so, be not preferred for making the nonwovens 110 that constitutes by glass fibre 111,112 used in the present invention.On the other hand, in order to improve the heat-shielding performance of thickness direction, hope glass fibre 111, be interweaved between 112 and lack.
Therefore, as the paper making machine that the nonwovens 110 that is made up of glass fibre 111,112 used in the present invention is manufactured paper with pulp, suitable use can be copied the oblique net formula paper making machine of paper with low input (inlet) concentration, but is not to be defined in this.
As the fiberglas chopped strand of one of inorfil used in the present invention preferably: fiber diameter is that 3～15 μ m, length of staple are that the component ratio of glass fibre 111,112 of 3～15mm is more than 99%.
Be described below, can predict fiber diameter less than 3 μ m or length of staple less than the fiberglas chopped strand of 3mm, be not suitable for constituting the nonwovens 110 of vacuum heat insulation material of the present invention with core material 100.
Fiber diameter,, produces between fiber bending and the fiber and is interweaved when utilizing wet type to copy paper manufactured nonwovens 110 because the rigidity of fiber is little less than the glass fibre of 3 μ m 111,112, and the area of contact between the fiber is increased.Therefore transmission of heat increases, and causes the heat-shielding performance variation of core material 100, so fiber diameter is not preferred less than the glass fibre 111,112 of 3 μ m.
Copy paper method and making under the situation of nonwovens 110 less than the glass fibre 111,112 of 3mm utilizing wet type with length of staple; When making the fiber dispersion that is positioned at the upper strata on the fiber that has disperseed that is positioned at lower floor the time; The fiber on upper strata can not overlap with the fiber of lower floor; Increased top fiber and be bearing in the possibility on lower floor's fiber with a bit, for example it is contemplated that an end of top fiber hangs down into lower floor, the other end is to locate to the outstanding mode of thickness direction.Like this, when certain bar fiber becomes between the many fibers during along the state of thickness direction overlap joint, produce transmission of heat along the length direction of fiber, and the area of contact between the fiber increases.Transmission of heat increases thus, makes the heat-shielding performance variation of core material 100, so length of staple is not preferred less than the glass fibre of 3mm.
If using fiber diameter is that the above glass fibre 111,112 of 15 μ m constitutes nonwovens 110; And carry out the range upon range of core material 100 that forms to many nonwovens 110; Then the fiber number of plies of core material 100 on thickness direction reduces; Heat conduction path on the thickness direction is shortened, and when forming nonwovens 110, it is big that the emptying aperture diameter becomes.Therefore, owing to receive the influence of gas, the heat-shielding performance of core material 100 is reduced, so the glass fibre of fiber diameter more than 15 μ m is not preferred to thermal conductivity.
If use the glass fibre 111,112 of length of staple more than 15mm; Then because length of staple is excessive with respect to fiber diameter; Crooked easily so the rigidity of fiber reduces, and produce being interweaved between the fiber, the area of contact between the fiber is increased.Therefore, transmission of heat increases, and makes the heat-shielding performance variation of core material 100, so the glass fibre of length of staple more than 15mm is not preferred.
The grammes per square metre of the nonwovens 110 that constitutes by glass fibre 111,112 that vacuum heat insulation material of the present invention is adopted with core material 100, preferably 30～600g/m 2In the grammes per square metre of nonwovens 110 less than 30g/m 2Situation under because the aperture diameter that exist in the nonwovens 110 are big, so gas is big to the influence of thermal conductivity.Therefore, the heat-shielding performance of core material 100 reduces, and the intensity of core material 100 diminishes, so the grammes per square metre of nonwovens 110 is less than 30g/m 2Be not preferred.On the other hand, if the grammes per square metre of nonwovens 110 surpasses 600g/m 2, the drying efficiency when then making nonwovens 110 owing to use glass fibre 111,112 reduces, and the productivity reduction, so be not preferred.
So-called grammes per square metre generally is meant the unit of measurement of paper thickness, representes the quality of every square metre paper, is also referred to as every square metre weight.Unit as metering nonwovens 110 thickness uses grammes per square metre here, and this nonwovens 110 is made up of the glass fibre 111,112 that utilizes wet type to copy the paper manufactured.
For example open in the record of 2006-17169 number (patent documentation 2) the open communique spy of Japan Patent, the average diameter that preferably constitutes the inorfils such as glass wool of vacuum heat insulation material core material is 1～5 μ m.And record, if the average diameter of this inorfil surpasses 5 μ m, the heat-shielding performance of the vacuum heat insulation material that then finally obtains itself reduces.The diameter of the inorfil of formation core material is more little, can improve the heat-shielding performance of vacuum heat insulation material really more.But thin inorfil price is high, and when utilizing wet type to copy paper manufactured nonwovens, has the shortcoming that dewatering efficiency reduces, productivity reduces.And in the present invention; About the adhering state between fiber parameters such as the fiber diameter of inorfil, length of staple and the fiber; As long as through selecting to be used to improve the optimum condition of heat-shielding performance; Even adopt the example of the bigger fiberglas chopped strand of fiber diameter, also can obtain heat-shielding performance far above the vacuum heat insulation material 1 of vacuum heat insulation material in the past as inorfil.
In addition, even use the fiberglas chopped strand of fiber diameter less than 6 μ m, the increase rate of the vacuum heat insulation material heat-shielding performance that finally obtains is compared with the situation of the fiberglas chopped strand that uses fiber diameter 10 μ m, also almost can ignore.Therefore, consider that from productivity, price, aspect of performance the fiber diameter of fiberglas chopped strand is 6～15 μ m preferably.Under the situation of the glass fibre 111,112 that uses this scope, can obtain heat-shielding performance with suitable manufacture cost than in the past the high vacuum heat insulation material 1 of vacuum heat insulation material.
Use has the core material 100 of above-mentioned characteristic, utilizes known method can make vacuum heat insulation material 1 of the present invention.Representative method is: in the structure of vacuum heat insulation material shown in Figure 11, be housed in core material 100 200 inside of the outsourcing material with barrier properties for gases that form bag shape.The outsourcing material 200 of under decompression state, accommodating core material 100 has high gas-obstructing character, and has hot sealing layer and for the protective layer that crack etc. is protected, can make for a long time to keep decompression states in the outsourcing material 200.In addition, also can be used as outsourcing material 200 to many pellicular cascades with above-mentioned characteristic.
Example as outsourcing material 200 concrete structures can be given an example: the ethylene-vinyl alcohol copolymer resin that making outermost surface is PETG (PET) resin, use has the aluminium-vapour deposition layer in the mesosphere, innermost layer are for using the gas barrier film of high-density polyethylene resin; Perhaps outermost surface uses nylon, mesosphere to use aluminium-vapour deposition PET resin and aluminium foil is two-layer, innermost layer is for the gas barrier film that uses high-density polyethylene resin etc.
In addition, for the initial heat-shielding performance that keeps vacuum heat insulation material 1 and heat-shielding performance as time passes, preferably at sorbents such as vacuum heat insulation material 1 inner using gases sorbent, moisture adsorbent.
Embodiment
Describe in the face of several embodiments of the present invention down, but the present invention is not limited thereto.
(embodiment 1～5, comparative example 1)
Is fiber diameter that 10 μ m, average fiber length are that the fiberglas chopped strand (be オ one ウ エ Application ス コ one ニ Application グ company (Owens Corning Corporation) make) of 10mm is put in the water; The concentration that makes fiberglas chopped strand is 0.5 quality %; Add the エ マ ノ one Application (Emanon as dispersing agent of 1 mass parts with respect to the fiberglas chopped strand of 100 mass parts; TM trade mark) 3199 (Kao Corp's manufacturings) are through stirring the slip that has prepared fiberglas chopped strand.
The slip of the fiberglas chopped strand that use obtains utilizes wet type to copy the paper method and manufactures paper with pulp, and has prepared reticulated work.The suitable fluid binder of tackiness agent kind shown in the dilution table 1 and therein with the reticulated work impregnation that obtains, and the moisture that reticulated work absorbs adjusted, make nonwovens become the binder content shown in the table 1.After this, dry through making reticulated work, process the nonwovens 110 that vacuum heat insulation material is adopted with core material 100.The grammes per square metre and the binder content of the nonwovens 110 that obtains are as shown in table 1.
In addition, in the tackiness agent kind of record, propylene liguid is acrylic emulsion (Dainippon Ink. & Chemicals Inc makes GM-4) in table 1, and liquid PVA is the PVA aqueous solution (making PVA117 to the Network ラ レ of Co., Ltd. is dissolved in the warm water).
(comparative example 2～4)
Adopt embodiment 1～5, comparative example 1 employed fiberglas chopped strand, utilize the slip that has prepared fiberglas chopped strand with embodiment 1～5, comparative example 1 identical method.
Add granular PVA (ユ ニ チ カ Co., Ltd. make OV-N) in the water to and stir, making its concentration is 10%, thereby has prepared granular binder slurry.
In the fiberglas chopped strand slip that obtains, add granular binder slurry,, use through mixing the slip that obtains, utilizing wet type to copy the paper method to manufacture paper with pulp, prepared reticulated work so that the content of tackiness agent is as shown in table 1 with respect to nonwovens.After this, through making the reticulated work that obtains dry, prepared the nonwovens 110 that vacuum heat insulation material is adopted with core material 100.The grammes per square metre and the binder content of the nonwovens 110 that obtains are as shown in table 1.
(example in the past)
As the employed core material of vacuum heat insulation material in the past, prepared nonwovens as laminar fiber assembly, this laminar fiber assembly is made up of the glass wool with the fiber diameter shown in the table 1.
In addition,, remove organic principle, obtain the binder content shown in the table 1 according to the following formula that utilizes of poor quality before and after the heating through heating vacuum heat insulation material 30 minutes under 600 ℃ temperature with core material 100 employed nonwovens 110.
Binder content (quality %)=[{ (quality before the heating)-(quality after the heating) }/(quality before the heating)] * 100
Carry out 10 nonwovens of making through above embodiment 1～5, comparative example 1～4 110 range upon range of, make core material 100.Across separator, on the upper and lower surfaces of each core material 100 that constitutes by the duplexer that obtains, apply 1kgf/cm respectively along thickness direction 2The pressure of (about 98kPa), in this state, maintenance degree of vacuum is the vacuum state of 0.01Torr (about 1.3Pa).In each core material 100 under this maintenance vacuum steady state, the hot-fluid through the upper and lower surfaces temperature partly of measuring each core material 100 that is made up of duplexer and each core material 100 of flowing through calculates thermal conductivity.The measurement result of the thermal conductivity that expression obtains in " thermal conductivity " hurdle of table 1.In addition, about example in the past, the thermal conductivity of the nonwovens that expression is made up of in the past glass wool in " thermal conductivity " hurdle of table 1.
Table 1
Can find out that from the result shown in the table 1 thermal conductivity of the vacuum heat insulation material 1 of the embodiment of the invention 1～5 and can the industrialization steady production below 0.85mW/mK.
In contrast, though the vacuum heat insulation material 1 of comparative example 1,2 can the industrialization steady production, thermal conductivity is respectively 1.50mW/mK and 0.90mW/mK.In addition; In comparative example 3, though can obtain the vacuum heat insulation material that thermal conductivity is 0.80mW/mK, in making nonwovens operation and the operation that is cut into nonwovens 110 with the outsourcing material 200 consistent sizes of vacuum heat insulation material 1; The phenomenon that glass fibre 111,112 comes off from the surface of nonwovens 110 in a large number takes place; In addition, produce disconnected paper phenomenon during owing to transmission between roller, so be difficult to stably make.In comparative example 4; Though can obtain thermal conductivity is the vacuum heat insulation material 1 of 0.60mW/mK; But the operation of removing tackiness agent needs the long period, in addition, and in the operation of outsourcing material 200 inside that are sealing into the core material 100 that constitutes by nonwovens 110 vacuum heat insulation material 1; Make nonwovens 110 shapes at random easily, so be difficult to industrial mass production.In addition, in the past the thermal conductivity of vacuum heat insulation material is 1.70mW/mK.
Therefore, the vacuum heat insulation material of the application of the invention can industrialization, vacuum heat insulation material that production heat-shielding performance stably is good, and the equipment such as refrigerator with good energy-efficient performance can be provided.
More than disclosed mode of execution and embodiment be illustration, the present invention is not limited thereto.Scope of the present invention is not limited to the above-described embodiment and examples, but representes with claim, and comprises content and all modifications that in the claim scope, carries out or the distortion that is equal to claim.
Industrial applicibility
Vacuum heat insulation material of the present invention with core material and vacuum heat insulation material through using many inorfils that utilize continuous filament method to make at least; The thermal conductivity of core material is reduced; And has good heat-shielding performance; Surmounted any improvement of in the past the thermal insulation the subject of knowledge and the object of knowledge being done, needed in the heat insulation equipment such as household refrigerator so be widely used in.

Claims (7)

1. a vacuum heat insulation material is cascaded by many nonwovens (110) with core material (100), it is characterized in that,
Said nonwovens (110) comprises many inorfils (111,112) that utilize continuous filament method to make at least,
In said nonwovens (110), the most of inorfil in said many inorfils (111,112) with the surperficial substantially parallel direction of said nonwovens (110) on extend,
There is the adhesive ingredients of relatively small amount in the adhesive ingredients that in the skin section of said nonwovens (110), has relative volume in the inside of said nonwovens (110).
2. vacuum heat insulation material according to claim 1 is characterized in that with core material (100), the content of said adhesive ingredients with respect to said nonwovens (110) more than the 0.1 quality %, below the 1.5 quality %.
3. vacuum heat insulation material according to claim 1 is with core material (100); It is characterized in that; The fiber diameter of said inorfil (111,112) is more than the 3 μ m, below the 15 μ m, and the average fiber length of said inorfil (111,112) is more than the 3mm, below the 15mm.
4. vacuum heat insulation material according to claim 1 is characterized in that with core material (100) said inorfil (111,112) is a glass fibre.
5. a vacuum heat insulation material (1) is characterized in that comprising:
Outsourcing material (200); And
Core material (100) is housed in the inside of said outsourcing material (200),
The inside of said outsourcing material (200) can keep being in decompression state,
Said core material (100) comprises that at least a described vacuum heat insulation material of above claim 1 uses core material.
6. a vacuum heat insulation material is characterized in that comprising the steps: with the production method of core material (100)
At least use many inorfils (111,112) and fluid binder, utilize wet type to copy the step that the paper method is made nonwovens (110); Said many inorfils (111,112) utilize the continuous filament method manufacturing; In said step, make in said many inorfils most of inorfil (111,112) with the surperficial substantially parallel direction of the said nonwovens of making (110) on extend; And
The said nonwovens of polylith (110) is carried out range upon range of step.
7. the production method of a vacuum heat insulation material (1) is characterized in that comprising the steps:
At least use many inorfils (111,112) and fluid binder, utilize wet type to copy the step that the paper method is made nonwovens (110); Said many inorfils (111,112) utilize the continuous filament method manufacturing; In said step, make in said many inorfils most of inorfil (111,112) with the surperficial substantially parallel direction of the said nonwovens of making (110) on extend;
Many said nonwovens (110) are carried out range upon range of step; And
Many after range upon range of said nonwovens (110) are housed in the inside of outsourcing material (200) and make the inside of said outsourcing material (200) keep being in the step of decompression state.
CN201080013026.XA 2009-03-27 2010-03-26 Core material for vacuum insulation material, vacuum insulation material, and processes for producing these Expired - Fee Related CN102362115B (en)

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CN105102874A (en) * 2013-04-05 2015-11-25 三菱电机株式会社 Vacuum heat-insulating material, thermal insulation tank provided with same, thermal insulator, and heat pump hot water heater
CN106015838A (en) * 2015-11-23 2016-10-12 福建赛特新材股份有限公司 Inner core material used for vacuum heat-insulating plate and vacuum heat-insulating plate
CN106015839A (en) * 2015-11-23 2016-10-12 福建赛特新材股份有限公司 Manufacturing method of inner core material used for vacuum heat-insulating plate and vacuum heat-insulating plate
CN107399426A (en) * 2017-07-21 2017-11-28 苏州市君悦新材料科技股份有限公司 A kind of aviation heat-insulation and heat-preservation module
CN109972284A (en) * 2018-05-11 2019-07-05 上海邦季新材料有限公司 A kind of preparation method of vacuum insulation panel glass fiber core material

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CN104937322A (en) * 2013-01-16 2015-09-23 乐金华奥斯有限公司 Core member for a vacuum insulation material including glass fibers, manufacturing method thereof, and vacuum insulation material using same
CN105102874A (en) * 2013-04-05 2015-11-25 三菱电机株式会社 Vacuum heat-insulating material, thermal insulation tank provided with same, thermal insulator, and heat pump hot water heater
CN105102874B (en) * 2013-04-05 2016-12-21 三菱电机株式会社 Vacuumed insulation panel and possess the cool-bag of this Vacuumed insulation panel, thermal insulator and heat pump hot-water supply system
CN106015838A (en) * 2015-11-23 2016-10-12 福建赛特新材股份有限公司 Inner core material used for vacuum heat-insulating plate and vacuum heat-insulating plate
CN106015839A (en) * 2015-11-23 2016-10-12 福建赛特新材股份有限公司 Manufacturing method of inner core material used for vacuum heat-insulating plate and vacuum heat-insulating plate
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CN107399426A (en) * 2017-07-21 2017-11-28 苏州市君悦新材料科技股份有限公司 A kind of aviation heat-insulation and heat-preservation module
CN109972284A (en) * 2018-05-11 2019-07-05 上海邦季新材料有限公司 A kind of preparation method of vacuum insulation panel glass fiber core material

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