CN102362115B - 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 PDFInfo
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- CN102362115B CN102362115B CN201080013026.XA CN201080013026A CN102362115B CN 102362115 B CN102362115 B CN 102362115B CN 201080013026 A CN201080013026 A CN 201080013026A CN 102362115 B CN102362115 B CN 102362115B
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- nonwovens
- core material
- heat insulation
- vacuum heat
- insulation material
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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
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- 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
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- 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
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
Technical field
The present invention relates to core material for vacuum heat insulation material, vacuum heat insulation material and their manufacture method.
background technique
In the past, for various food is heated, cooling, insulation and the refrigerator that uses, cooler bin, HEATING BOX etc., use the thermal-protective material with various structures or performance.Due 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.After generally by the core material being formed by inorganic material, being filled into the inside of outsourcing material, outsourcing material being sealed, and make the inside of outsourcing material remain in decompression state, thereby can obtain vacuum heat insulation material.In inorganic material, the glass wool that adopts the glass fibre by flame method or centrifuge method manufacture to form, form the core material of above-mentioned vacuum heat insulation material.
For example the vacuum heat insulation material of Japanese Patent Publication communique JP No. 2005-265038 (patent documentation 1) record is that glass wool that the glass fibre by as inorfil is formed carries out wet type and manufactures paper with pulp, and using multiple stacked use as core material afterwards of the inorfil thin slice that obtains, the particle of particle diameter in inorfil more than 30 μ m contains ratio below 0.1 quality %, average fibre diameter in 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 of No. 2006-17169 (patent documentation 2) record of Japanese Patent Publication communique JP forms glass wool by the glass fibre as the inorfil stacking material, core material consists of this glass wool, the core material reduced pressure sealing, in outsourcing material inside, the density of the core material in vacuum heat insulation material is 200～270kg/m
3, the core material of opening after outsourcing material includes the glass fibre of length of staple more than 100 μ m more than 75%.
Patent documentation 1: No. 2005-265038, Japanese Patent Publication communique JP
Patent documentation 2: No. 2006-17169, Japanese Patent Publication communique JP
summary of the invention
Fig. 8 schematically shows in the past in the glass wool that the core material as vacuum heat insulation material adopts, the planimetric map of the distribution of glass fibre.Fig. 9 is plane electronics photomicrograph (100 times of magnification factor), its means in the past in glass wool that the core material as vacuum heat insulation material adopts, distribution before glass fibre is compressed, Figure 10 means the section electron micrograph (100 times of magnification factors) of same distribution state.
As shown in Figure 8, can find out in glass wool 500, many glass fibres 510 of various length of staple extend and random distribution to all directions.In addition, as shown in Figure 8, Figure 9, in the glass wool that utilizes flame method or centrifuge method to manufacture, with respect to main fibre, sneaked into short fibre and the fiber diameter microfibre 1 μ m below of length of staple below 1mm.Above-mentioned short fibre or microfibre are filled between main fibre or interweave between main fibre, produce hot conduction between fiber, can think that institute is so that the heat-shielding performance reduction owing to causing the heat conduction 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 forming in the above described manner glass wool, so as No. 2005-265038 (patent documentation 1) record of Japanese Patent Publication communique JP, 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 with respect to sheet surface, also be difficult to arrange most glass fibre.
In addition, as No. 2006-17169 (patent documentation 2) record of Japanese Patent Publication communique JP, even press glass wool, the core material density that makes to include the glass fibre of length of staple more than 100 μ m more than 75% reaches 200～270kg/m
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 the heat-shielding performance reduction caused because producing the heat conduction between fiber.And the thermal conductivity of the vacuum heat insulation material obtained is limited in the 2mW/mK left and right so utilization improvement way in the past improves the heat-shielding performance of vacuum heat insulation material.
The object of the present invention is to provide core material for vacuum heat insulation material, there is the vacuum heat insulation material of core material and their manufacture method for this vacuum heat insulation material, described vacuum heat insulation material has good heat-shielding performance 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.
The present inventor is in order to solve the problem of the core material existence that vacuum heat insulation material adopted in the past, repeatedly carried out wholwe-hearted research, it found that: forming vacuum heat insulation material with in the fiber of core material, at least include and utilize many inorfils of continuous filament method manufacture just can realize above-mentioned purpose by making.Wherein, so-called continuous filament method is a kind of fibre manufacture, by being made 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 characteristics with core material.
Vacuum heat insulation material of the present invention forms by multiple nonwovens are stacked with core material.Nonwovens at least comprises many inorfils that utilize continuous filament method to manufacture.In nonwovens, on the direction substantially parallel on the surface with nonwovens of the most of inorfil in many inorfils, 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 manufactures very high.Therefore, by handle, utilize many inorfils of continuous filament method manufacture to cut into substantially certain length, can the state very high at straightness accuracy under, obtain the very little and length of fiber diameter difference identical many inorfils substantially.
Because the nonwovens that forms core material of the present invention at least includes many inorfils that utilize continuous filament method to manufacture, so when with above-mentioned many inorfils, forming nonwovens, if each inorfil is arranged on the direction parallel with respect to the surface of nonwovens, can easily arrange many inorfils, so that extend on the most inorfil direction substantially parallel on the surface with nonwovens.Now, although the major part of many inorfils is substantially extended on parallel direction on the surface with nonwovens, be not mutually to be closely arranged on parallel direction, but in the plane that forms nonwoven surface towards the random direction dispersed arrangement.Therefore, can reduce the inorfil be filled between many inorfils that form core material as far as possible, and can reduce the inorfil interweaved between many inorfils as far as possible, so can prevent from producing the heat conduction between inorfil.Thus, by preventing producing the heat conduction along the core material thickness direction, can make the thermal conductivity of core material reduce, the vacuum heat insulation material obtained 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.
Vacuum heat insulation material at said structure is that adopt with core material, for example, in nonwovens that consist of glass fibre, do not have the combination force between fiber.Therefore, in order to prevent that in the manufacturing process of nonwovens glass fibre from coming off, and, in order to prevent that in the manufacturing procedure of subsequent handling shape is at random, need to use tackiness agent in the copy paper operation.
Liquid tackiness agent easily concentrates on around the crossover sites of many glass fibres because of surface tension.Therefore, though between adjacent glass fibre in a contact condition, also have the possibility around this contact position of adhesive coverage.Can expect thus to produce the heat conduction by tackiness agent, so can think that liquid tackiness agent is not preferred.Therefore, consider to use granular or fibrous tackiness agent.
Make tackiness agent at use granular tackiness agent or fibre adhesive, and these tackiness agents are disperseed to be blended in fiberglas chopped strand, utilize the wet type copy paper method to manufacture in the situation of nonwovens, can think that most tackiness agent is positioned at beyond the point of contact of fiber, and be overlapped between fiber by tackiness agent.Be envisioned that above-mentioned overlap joint is extremely very thin, produces heat conducting possibility very little.But, for heat-shielding performance is brought up to ultimate state, need to suppress the heat conduction caused because of above-mentioned tackiness agent.
Therefore, for the small heat conduction that the tackiness agent prevented because riding between fiber causes, heat-shielding performance is brought up to ultimate state, can consider before vacuum seal, remove or reduce the tackiness agent in core material by the method for utilizing thermolysis, further improving heat-shielding performance.
; can consider before core material is sealing into to outsourcing material inside; high and be compared at the low-melting temperature of the glass fibre that one of inorfil uses and processed by the heat decomposition temperature at the specific viscosity mixture, utilize thermolysis only binder removal.In addition, in the situation that such as using the water-soluble resin tackiness agents such as polyvinyl alcohol (PVA) as tackiness agent, except said method, can consider to utilize warm water etc. to clean to remove or reduce tackiness agent.
But, remove the tackiness agent in core material in order to utilize said method, not only need long heating process or washing process, and it is very low to remove the intensity of the core material after tackiness agent, so the operation that core material is sealing into to outsourcing material inside also needs the time.Therefore, although obtain the extraordinary vacuum heat insulation material of heat-shielding performance, cause being difficult to utilizing the manufacturing equipment of vacuum heat insulation material in the past to carry out the new problem of industrial mass production.
The present inventor is in order to address the above problem, repeatedly carried out wholwe-hearted research, it found that: at vacuum heat insulation material, use in core material, make forming vacuum heat insulation material with in the fiber of core material, at least include many fibers that utilize continuous filament method to manufacture, by using the minute quantity fluid binder as tackiness agent, can solve above-mentioned new problem.Wherein, so-called fluid binder is to instigate adhesive ingredients to dissolve and become liquid state or make the adhesive ingredients emulsion and become liquid state.
In the situation that use granular or fibre adhesive, for the heat conduction that suppresses to cause because of adhesive ingredients, if the adhesive ingredients content in nonwovens is reduced to ultimate state, because adhesive ingredients is uniformly distributed in nonwovens, so strength decreased not only, and fiber easily comes off from the surface of nonwovens, during the fiber come off is attached to drying equipment in a large number, produce bad phenomenon such as being difficult to carry out production continuously in manufacturing the nonwovens operation.
On the other hand, the present inventor finds: in the situation that use fluid binder, even the content of the adhesive ingredients in nonwovens is considerably less, with the situation of having used granular or fibre adhesive, compare, also not only can obtain sufficient intensity required in producing continuously, and heat-shielding performance is good.Its reason is presumed as follows:
In the heat drying operation of fluid binder when manufacturing nonwovens, when the moisture of the netted thing of nonwovens inside evaporates, tackiness agent also moves together, so tackiness agent concentrates on two surfaces of nonwovens, produces the tendency that the tackiness agent of nonwovens inside tails off.
In addition, fluid binder causes around the crossover sites that easily concentrates on many fibers because of surface tension.Although this situation sees not to be preferred from reducing heat conducting angle, from putting forward high-intensity angle, sees it is preferred.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 nonwovens is considerably less, can make combination more securely between fiber owing to concentrating on two lip-deep tackiness agents of nonwovens, so improved whole intensity, also can obtain needed intensity in manufacturing the nonwovens operation and manufacturing the vacuum insulation material material process.
In addition, due in nonwovens inside, the content of adhesive ingredients than the surface of nonwovens still less, so the heat of being undertaken by tackiness agent conduction is considerably less.
For these reasons, in the situation that use the minute quantity fluid binder, due to mutually bonding between near the fiber that can effectively make nonwoven surface, so vacuum heat insulation material of the present invention has and can meet the desired enough intensity of industrial mass production with core material, on the other hand, can make the amount of tackiness agent of nonwovens inside considerably less.
In addition, in the situation that use granular or fibre adhesive, the phenomenon that tackiness agent moves in nonwovens in the heat drying operation as fluid binder can occur hardly.
Above discovery based on the inventor, vacuum heat insulation material of the present invention has following feature with core material.
Vacuum heat insulation material of the present invention forms by multiple nonwovens are stacked with core material.Nonwovens comprises many inorfils that utilize continuous filament method to manufacture, the fiber diameter of described inorfil is more than 3 μ m, below 15 μ m, the average fiber length of described inorfil is more than 3mm, below 15mm, and the straightness accuracy of described inorfil is very high.In nonwovens, in the two-layer inorganic fibre mat of described nonwovens inner stacks, form the most of inorfil in described many inorfils on upper strata and form on most of inorfil in described many inorfils of lower floor direction substantially parallel on the surface with described nonwovens and extend, but not that mutual close-packed arrays is on parallel direction, but some contact between adjacent fiber, and in the Ge plane, the upper and lower that forms nonwovens towards the random direction dispersed arrangement.With in core material, there is the fluid binder composition of relative volume at the vacuum heat insulation material with said structure in the skin section of nonwovens, have the fluid binder composition of relatively small amount in the inside of nonwovens.
At vacuum heat insulation material of the present invention with in core material, preferably: the content of adhesive ingredients with respect to nonwovens more than 0.1 quality %, below 1.5 quality %.
If adhesive ingredients content is less than 0.1 quality %,, due to strength deficiency in manufacturing the nonwovens operation and manufacturing the vacuum insulation material material process, produce in a large number the phenomenon that fiber comes off or disperses from nonwoven surface, so be difficult to industrial mass production.In addition, if adhesive ingredients content surpasses 1.5 quality %, with the situation of using granular or fibre adhesive, compare, vacuum heat insulation material is equal extent or following by the core material heat-shielding performance, can not obtain using the effect of fluid binder.
At vacuum heat insulation material of the present invention, with in core material, preferably: the fiber diameter of inorfil is more than 3 μ m, below 15 μ m, and the average fiber length of inorfil is more than 3mm, below 15mm.In this case, the thermal conductivity of core material can be reduced to greatest extent, thereby the vacuum heat insulation material core material of good heat-shielding performance can be obtained having.
At vacuum heat insulation material of the present invention, with in core material, preferably: inorfil is glass fibre.In this case, for example, because other inorfils of thermal conductivity ratio of glass fibre are little, less than ceramic fiber, so, by reducing the thermal conductivity of material self, can further improve the heat-shielding performance of core material.
Vacuum heat insulation material of the present invention comprises outsourcing material and is housed in the core material of outsourcing material inside.The within of outsourcing material remains in decompression state.Core material at least comprises a vacuum heat insulation material core material with above-mentioned any one feature.
Vacuum heat insulation material of the present invention comprises the steps: at least with many inorfils and fluid binder, utilizes the wet type copy paper method to manufacture the step of nonwovens by the manufacture method of core material, above-mentioned many inorfils utilize the continuous filament method manufacture, in described step, make to extend on most of inorfil in many inorfils direction substantially parallel in the nonwoven surface with manufacturing; And multiple nonwovens are carried out to stacked step.
With in the manufacture method of core material, at least use many inorfils and fluid binder at vacuum heat insulation material of the present invention, above-mentioned many inorfils utilize continuous filament method manufacture.When with above-mentioned many inorfils, utilizing the wet type copy paper method to manufacture nonwovens, if each inorfil is arranged on the direction parallel with respect to the surface of nonwovens, can easily make to arrange many inorfils, so that most inorfil extends on the direction substantially parallel with nonwoven surface.
Now, on the major part of many inorfils direction substantially parallel on the surface with nonwovens, extend, but be not mutual close-packed arrays on parallel direction, but in the plane that forms nonwoven surface towards the random direction dispersed arrangement.Thus, even stacked multiple nonwovens in order to form core material, owing to can reduce the inorfil be filled between many inorfils as far as possible, and can reduce the inorfil interweaved between many inorfils, so can prevent from being arranged in generation heat conduction between the inorfil on direction substantially parallel with nonwoven surface as far as possible.
In addition, in the drying process when manufacturing nonwovens, while following the water of nonwovens inside or solvent evaporation, to the surface of nonwovens, move, fluid binder concentrates in two top layers of nonwovens.Therefore, even the amount of the tackiness agent contained in nonwovens is few, also can improve the intensity of nonwoven surface, so the fiber that can suppress on nonwoven surface disperses, not only can obtain needed intensity in manufacturing the nonwovens operation and manufacturing the vacuum insulation material material process, and because the binder content of nonwovens inside further reduces, so the heat of being undertaken by tackiness agent conduction also becomes considerably less.
Therefore, by prevent producing the heat conduction along the core material thickness direction as far as possible, can make the thermal conductivity of core material reduce, thereby can obtain having the vacuum heat insulation material core 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, because even the amount of the tackiness agent contained in nonwovens is few, also there is needed intensity in manufacturing the nonwovens operation and manufacturing the vacuum insulation material material process, and the fiber that disperses or come off from nonwoven surface is few, so can obtain the vacuum heat insulation material core material as medium material that can the industrial mass production vacuum heat insulation material.
The manufacture method of vacuum heat insulation material of the present invention comprises the steps: at least with many inorfils and fluid binder, utilizes the wet type copy paper method to manufacture the step of nonwovens, above-mentioned many inorfils utilize the continuous filament method manufacture, in described step, make to extend on most of inorfil in many inorfils direction substantially parallel in the nonwoven surface with manufacturing; Multiple nonwovens are carried out to stacked step; And multiple nonwovens after stacked are housed in to the inside of outsourcing material and make the inside of outsourcing material remain in the step of decompression state.
In the manufacture method of vacuum heat insulation material of the present invention, at least use many inorfils and fluid binder, above-mentioned many inorfils utilize the continuous filament method manufacture.When with above-mentioned many inorfils, utilizing the wet type copy paper method to manufacture nonwovens, if each inorfil is arranged on the direction parallel with the surface of nonwovens, can easily arrange many inorfils, so that extend on the most inorfil direction substantially parallel on the surface with nonwovens.Now, although on the major part of many inorfils direction substantially parallel on the surface with nonwovens, extend, be not mutual close-packed arrays on parallel direction, but in the plane that forms nonwoven surface towards the random direction dispersed arrangement.Therefore, even stacked multiple nonwovens in order to form core material, owing to can reduce the inorfil be filled between many inorfils as far as possible, and can reduce the inorfil interweaved between many inorfils, so also can prevent from producing the heat conduction between inorfil as far as possible.By multiple nonwovens after stacked being housed in to the inside of outsourcing material, and make the inside of outsourcing material remain in decompression state, can manufacture vacuum heat insulation material.
In addition, because the content of the adhesive ingredients of nonwovens inside is considerably less, so the probability that adhesive ingredients is attached on the crossover sites of many inorfils is also very low.Therefore, the heat conduction of being undertaken by tackiness agent is few.
Like this, can prevent from producing the heat conduction along the core material thickness direction.Therefore, can make the thermal conductivity of core material reduce.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 small amount of tackiness agent makes between the fiber of nonwoven surface mutually bonding effectively.Therefore, can guarantee nonwovens needed intensity in manufacturing the nonwovens operation and manufacturing the vacuum insulation material material process.Thus, can the industrial mass production vacuum heat insulation material.
As mentioned above, according to the present invention, by at least using many inorfils and the fluid binder utilize that continuous filament method manufactures, can make the thermal conductivity of core material reduce, thereby core material and vacuum heat insulation material with this core material for the vacuum heat insulation material that can obtain having excellent adiabatic capacity, described 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, according to the present invention, owing to there being the adhesive ingredients of relative volume in the skin section of nonwovens, there is the adhesive ingredients of relatively small amount in the inside of nonwovens, so tackiness agent can make the fiber on two surfaces of nonwovens mutually bonding separately effectively, the heat conduction that not only can make to cause because of tackiness agent is considerably less, can also guarantee nonwovens needed intensity in manufacturing the nonwovens operation and manufacturing the vacuum insulation material material process, so can the industrial mass production vacuum heat insulation material.
The accompanying drawing explanation
Fig. 1 is the sectional view that schematically illustrates one embodiment of the present invention, (A) means the configuration of core material and outsourcing material, after (B) meaning the outsourcing material inner pressure relief, and the state of vacuum heat insulation material inside.
Fig. 2 is the stereogram that schematically illustrates one embodiment of the present invention, (A) means the configuration of core material and outsourcing material, after (B) meaning the outsourcing material inner pressure relief, and the state of vacuum heat insulation material inside.
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 the core material that forms vacuum heat insulation material adopts.
Fig. 4 means the plane electronics photomicrograph (100 times of magnification factors) of one embodiment of the present invention, the distribution before the glass fibre of the nonwovens that the core material of expression formation vacuum heat insulation material adopts is compressed.
Fig. 5 means the section electron micrograph (100 times of magnification factors) of one embodiment of the present invention, the distribution before the glass fibre of the nonwovens that the core material of expression formation vacuum heat insulation material adopts is compressed.
Fig. 6 is the sectional view of a kind of manner of comparison of the present invention, schematically illustrates in the nonwovens that the core material of vacuum heat insulation material adopts 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 the core material of vacuum heat insulation material adopts the distribution of fluid binder on the nonwoven thickness direction.
Fig. 8 schematically illustrates in the past in the glass wool that the core material as vacuum heat insulation material adopts, the plan view of the distribution of glass fibre.
Fig. 9 is plane electronics photomicrograph (100 times of magnification factor), means in the past in glass wool that the core material as vacuum heat insulation material adopts the distribution before glass fibre is compressed.
Figure 10 is section electron micrograph (100 times of magnification factor), means in the past in glass wool that the core material as vacuum heat insulation material adopts 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
Below with reference to the accompanying drawings embodiments of the present invention are described.
Fig. 1 is the sectional view that schematically illustrates the vacuum heat insulation material structure of one embodiment of the present invention.(A) of Fig. 1 means the state before the outsourcing material inner pressure relief, and (B) of Fig. 1 means the state after the outsourcing material inner pressure relief.
As shown in Figure 1, in vacuum heat insulation material 1, core material 100 is housed in the inside of outsourcing material 200, and described outsourcing material 200 has barrier properties for gases and forms bag-shaped.
As shown in Fig. 1 (A), core material 100 is laminated by multiple nonwovens 110.Each layer of nonwovens 110 used the glass fibre of one of inorfil and a small amount of tackiness agent, utilizes copy paper method to make.
As shown in Fig. 1 (B), after the inner pressure relief of outsourcing material 200, utilize the external pressure of outsourcing material 200 to be compressed core material 100, multiple nonwovens 110 that form core material 100 are extruded 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 in the above described manner nonwovens, and form core material nonwovens is stacked, then core material is configured in to the inside of outsourcing material and is reduced pressure, form vacuum heat insulation material.
Fig. 2 is the stereogram that schematically illustrates one embodiment of the present invention, (A) means the configuration of core material and outsourcing material, after (B) meaning the outsourcing material inner pressure relief, and the state of vacuum heat insulation material inside.A part that has only meaned respectively each nonwovens, core material, outsourcing material.
As shown in Fig. 2 (A), stacked 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 forms bag-shapedly, covers whole core material 100.
As shown in Fig. 2 (B), if reduced pressure in the inside of bag-shaped outsourcing material 200, core material 100 is compressed.If core material 100 is compressed, multiple nonwovens 110 mutually push and contact.
The present inventor is for the heat-shielding performance of the vacuum heat insulation material 1 that improves said structure, carried out wholwe-hearted research, it found that by using the nonwovens 110 consisted of the 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 forms the core material 100 that vacuum heat insulation materials 1 adopt, and at least includes many inorfils and the fluid binder that utilizes that continuous filament method manufactures.
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 in decompression state, by stacked nonwovens 110, forms core material 100.Nonwovens 110 at least includes many inorfils and fluid binder, and above-mentioned many inorfils utilize the continuous filament method 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 in a large number fiber that described diameter is thin, in order to can consider and the little angle consideration from the thermal conductivity of raw material itself with the angle of lower price circulation, inorfil is preferably used glass fibre.
In one embodiment of the invention, using use cut into certain-length glass fibre, utilize nonwovens 110 that the wet type copy paper method manufactures to use as the core material 100 of vacuum heat insulation material.Wherein, the glass fibre that what is called cuts into certain-length refers to: utilize continuous filament method that molten glass is pulled out and is shaped from a plurality of nozzles, 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 to specific length.The precursor that cuts into like this glass fibre after specific length is called to fiberglas chopped strand.
Because the glass fibre obtained like this is, with certain size, continuous fiber is cut into to specific length, thus this glass fibre fiber that to be straightness accuracy high and rigidity is large, and there is substantially uniformly fiber diameter and be roughly circular section.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 manufactures very high.Therefore, by handle, utilize many inorfils of continuous filament method manufacture to cut into substantially certain length, can the state very high at straightness accuracy under, obtain the very little and length of fiber diameter difference identical many inorfils substantially.
Thus, in the situation that use this glass fibre to utilize the wet type copy paper method to manufacture nonwovens 110, can obtain following nonwovens 110:, although fiber extends on the direction parallel with the surperficial cardinal principle of nonwovens 110, fiber orientation random direction dispersed arrangement in the plane that forms nonwovens 110 surfaces.
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 the core material that forms vacuum heat insulation material adopts.Fig. 3 means the nonwovens consisted of the layer glass layer of fibers.Fig. 4 means the plane electronics photomicrograph (100 times of magnification factors) of one embodiment of the present invention, distribution before the glass fibre of the nonwovens that the core material of expression vacuum heat insulation material adopts is compressed, Fig. 5 means the section electron micrograph (100 times of magnification factors) of same distribution state.
As shown in Figure 3, many the glass fibres 111 that form upper strata extend with on many glass fibres 112 that the form lower floor direction parallel in the surface cardinal principle with nonwovens 110, but be not mutual close-packed arrays on parallel direction, but dispersed arrangement becomes towards random direction in forming the plane on nonwovens 110 surfaces.In addition, as shown in Figure 4, Figure 5, can find out that the straightness accuracy of each fiber is very high.And, although most fiber on the surface with nonwovens 110, substantially on parallel direction, extend, in the plane that forms nonwovens 110 surfaces towards the random direction dispersed arrangement.
As mentioned above, because the nonwovens 110 that forms core material 100 of the present invention at least includes many glass fibres as one of inorfil 111,112 that utilize continuous filament method to manufacture, so when using above-mentioned many glass fibres 111,112 to form nonwovens 110, if each glass fibre 111,112 is arranged on the direction parallel with respect to the surface of nonwovens 110, can easily arrange many glass fibres 111,112, so that most glass fibre 111,112 extends on the direction parallel with the surperficial cardinal principle of nonwovens 110.Now, although the major part of many glass fibres 111,112 is extended on the direction parallel with the surperficial cardinal principle of nonwovens 110, but be not mutual close-packed arrays on parallel direction, but in forming the plane on nonwovens 110 surfaces towards the random direction dispersed arrangement.Owing to can reduce the glass fibre be filled between many glass fibres 111,112 that form core material 100 as far as possible, and can reduce the glass fibre interweaved between many glass fibres 111,112, so can prevent from producing the heat conduction between glass fibre 111,112 as far as possible.Therefore, by preventing producing the heat conduction along core material 100 thickness directions, can make the thermal conductivity of core material 100 reduce, thereby core material 100 and vacuum heat insulation material 1 with this core material 100 for the vacuum heat insulation material that can obtain having excellent adiabatic capacity, described 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 mentioned above, core material of the present invention is made by nonwovens 110, the inorfil that forms this nonwovens 110 is continuous fiber to be cut off to the glass fibre with specific length 111,112 form 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, owing to being the some contact between each glass fibre 111,112, so can significantly suppress the heat conduction between glass fibre 111,112.
Although also can consider to adopt other raw material to carry out 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 preferred material.
In addition, the thermal conductivity of organic material is generally low than inorganic material, but there is no rigidity.Therefore, the position that organic fibrous material intersects at fiber makes fibre deformation because of external pressure, causes face contact between fiber or the minimizing of vacuum space ratio.Its result, core material is used the vacuum heat insulation material of organic fiber because thermal conductivity is high, so be not preferred material.
In the nonwovens 110 formed by glass fibre 111,112 adopted with core material 100 at vacuum heat insulation material of the present invention, there do not is the combination force between fiber.Therefore, come off in order to prevent glass fibre 111,112 in the manufacturing process at nonwovens 110, and, in order to prevent that in the manufacturing procedure of subsequent handling shape is at random, need to use tackiness agent in the copy paper operation.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 to be restricted to bottom line to the use amount of tackiness agent.
Following discovery based on the inventor, the tackiness agent in the present invention is not used granular or fibrous tackiness agent, and uses fluid binder.
The present inventor finds: in the situation that use fluid binder, even the content of the adhesive ingredients in nonwovens 110 is considerably less, with the situation of using granular or fibre adhesive, compare, also not only can obtain enough intensity required in producing continuously, and heat-shielding performance is good.Its reason is presumed as follows:
In the heat drying operation of fluid binder when manufacturing nonwovens 110, when the moisture of nonwovens 110 reticulated work inside evaporates, tackiness agent also moves together, so tackiness agent concentrates on two surfaces of nonwovens 110, produces the tendency that the tackiness agent of nonwovens 110 inside tails off.
In addition, fluid binder easily concentrates on around the crossover sites of many glass fibres 111,112 because of surface tension.Although this situation sees not to be preferred from reducing heat conducting angle, from putting forward high-intensity angle, sees it is preferred.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 nonwovens 110 is considerably less, also can make combination more securely between glass fibre 111,112 owing to concentrating on 110 two lip-deep tackiness agents of nonwovens, so improved bulk strength, can obtain needed intensity in the manufacturing process of the manufacturing process of nonwovens 110 and vacuum heat insulation material 1.
In addition, due in nonwovens 110 inside, the content of adhesive ingredients than the surface of nonwovens 110 still less, so the heat of being undertaken by tackiness agent conduction is considerably less.
For these reasons, in the situation that use the minute quantity fluid binder, due to mutually bonding between the glass fibre 111,112 that can effectively make nonwovens 110 near surfaces, 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 tackiness agent of nonwovens 110 inside 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 the core material of vacuum heat insulation material adopts 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 the core material of vacuum heat insulation material adopts the distribution of fluid binder on the thickness direction of nonwovens.In addition, in Fig. 6, the part shown in point means 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, in the situation that use granular or fibre adhesive, the adhesive ingredients that is expressed as point-like is dispersed on the thickness direction of nonwovens.In contrast, as shown in Figure 7, used in the present invention in 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 1.5 quality %.
In addition, although fluid binder also can be used inorganic bond, if but use inorganic bond, the crooked pliability of fiber assembly is poor, that is, the crooked pliability of nonwovens is poor, in addition, in the situation that use as product, because the cost that uses inorganic bond is 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 they are dissolved in to the solution in solvent; Or the aqueous solution of the water-soluble binders such as polyvinyl alcohol (PVA), starch etc., although so long as liquid state, with regard to there is no particular limitation, from the relation consideration of intensity and cost, is applicable to using emulsion acrylic resin or polyvinyl alcohol water solution etc.
In a kind of mode of execution at vacuum heat insulation material of the present invention by the manufacture method of core material 100, at first, at least with many glass fibres as one of inorfil 111,112 and fluid binder, utilize the wet type copy paper method to manufacture nonwovens 110, above-mentioned many glass fibres 111,112 utilize the continuous filament method manufacture.Thus, most of glass fibre 111,112 in many glass fibres is extended substantially on parallel direction on the surface of the nonwovens 110 with manufacturing.Then, stacked multiple nonwovens 110.
In addition, in a kind of mode of execution of the manufacture method of vacuum heat insulation material 1 of the present invention, at first, at least with many glass fibres 111,112 and fluid binder, utilize the wet type copy paper method to manufacture nonwovens 110, above-mentioned many glass fibres 111,112 utilize the continuous filament method manufacture.Thus, most of glass fibre 111,112 in many glass fibres is extended substantially on parallel direction on the surface of the nonwovens 110 with manufacturing.Then, stacked multi-layer nonwoven fabrics 110.After this, multiple nonwovens 110 after stacked are housed in to the inside of outsourcing material 200, make outsourcing material 200 inside remain in decompression state.
In addition, in a kind of mode of execution at vacuum heat insulation material of the present invention by the manufacture method of core material 100 or vacuum heat insulation material 1, preferably use the emulsion of above-mentioned resin, the fluid binders such as the aqueous solution of above-mentioned resin, and preferably adopt following method: first-class with the vaporific glass fibre 111,112 that is sprayed on this fluid binder by sprayer etc., fluid binder is attached on glass fibre 111,112.
In a kind of mode of execution of the manufacture method of vacuum heat insulation material of the present invention, at least use many glass fibres 111,112 and fluid binder, above-mentioned many glass fibres 111,112 utilize the continuous filament method manufacture.When with above-mentioned many glass fibres 111,112, utilizing the wet type copy paper method to manufacture nonwovens 110, if each glass fibre is arranged on the direction parallel with respect to the surface of nonwovens 110, can easily arrange many glass fibres, so that extend on most glass fibre 111,112 direction substantially parallel on the surface with nonwovens 110.Now, although extend on the major part of many glass fibres 111,112 direction substantially parallel on the surface with nonwovens 110, but be not mutual close-packed arrays on parallel direction, but in forming the plane on nonwovens 110 surfaces towards the random direction dispersed arrangement.Therefore, even stacked multiple nonwovens 110 in order to form core material 100, owing to can reduce the glass fibre be filled between many glass fibres as far as possible, and can reduce the glass fibre interweaved between many glass fibres, so also can prevent from producing the heat conduction between glass fibre as far as possible.In addition, be housed in the inside of outsourcing material 200 by multiple nonwovens 110 stacked, and make the inside of outsourcing material 200 remain in decompression state, can manufacture vacuum heat insulation material 1.Thus, by preventing producing the heat conduction along core material 100 thickness directions, can make the thermal conductivity of core material 100 reduce, thereby the vacuum heat insulation material 1 that can obtain having the core material 100 of excellent adiabatic capacity and have this core material 100, described 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 the wet type copy paper method to manufacture the nonwovens 110 formed by glass fibre 111,112 used in the present invention.In the wet type copy paper method, by adding suitable dispersing agent, make to cut off with certain-length the fiberglas chopped strand monofilament that glass fibre forms, and decentralized configuration becomes stratiform, can obtain the nonwovens 110 formed by stranded less glass fibre 111,112.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, there is high compression-strength and the low-down nonwovens 110 of thermal conductivity owing to producing on thickness direction, so above-mentioned nonwovens 110 is suitable as the core material 100 of vacuum heat insulation material 1 very much.
In manufacture method of the present invention, adopt the wet type copy paper method to be manufactured paper with pulp to nonwovens 110, this known paper making machines such as can using fourdrinier paper machine, short net paper making machine, oblique net formula paper making machine of manufacturing paper with pulp.
Usually, the nonwovens consisted of glass fibre is as the thermal-protective material or the electrical insulator that have stable on heating thermal-protective material, have refractory nature.Therefore, because need to having, nonwovens can bear the intensity of pulling open or puncturing etc., so mostly need to be interweaved between fiber.The nonwovens consisted of the glass fibre for such use utilizes the copy paper method manufacture to form mostly, and this copy paper method is used fourdrinier paper machine, short net paper making machine.
And the nonwovens 110 consisted 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 easily making the copy paper method that fiber direction is consistent that area of contact between fiber is increased, so, for manufacturing the nonwovens 110 formed by glass fibre 111,112 used in the present invention, be not preferred.On the other hand, in order to improve the heat-shielding performance of thickness direction, wish between glass fibre 111,112 to be interweaved few.
Therefore, as the paper making machine that the nonwovens 110 consisted of glass fibre 111,112 used in the present invention is manufactured paper with pulp, applicable use can be carried out to hang down input (inlet) concentration the oblique net formula paper making machine of copy paper, but is not to be defined in this.
As the fiberglas chopped strand of one of inorfil used in the present invention preferably: the component ratio that fiber diameter is 3～15 μ m, the length of staple glass fibre 111,112 that is 3～15mm is more than 99%.
As described below, can predict fiber diameter and be less than the fiberglas chopped strand that 3 μ m or length of staple are less than 3mm, be not suitable for forming the nonwovens 110 of vacuum heat insulation material of the present invention with core material 100.
Fiber diameter is less than the glass fibre 111,112 of 3 μ m because the rigidity of fiber is little, when utilizing the wet type copy paper method to manufacture nonwovens 110, produces between fiber bending and fiber and is interweaved, and the area of contact between fiber is increased.Therefore the heat conduction increases, and causes the heat-shielding performance variation of core material 100, so fiber diameter is less than the glass fibre 111,112 of 3 μ m, is not preferred.
In the situation that utilize the wet type copy paper method and manufacture nonwovens 110 with the glass fibre 111,112 that length of staple is less than 3mm, when the fiber dispersion that makes to be positioned at upper strata on the fiber disperseed that is positioned at lower floor the time, the fiber on upper strata can not overlap with the fiber of lower floor, increase top fiber and be bearing in the possibility on lower floor's fiber with a bit, an end that for example it is contemplated that top fiber hangs down into lower floor, and 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, along the length direction generation heat conduction of fiber, and the area of contact between fiber increases.The heat conduction increases thus, makes the heat-shielding performance variation of core material 100, so length of staple is less than the glass fibre of 3mm, is not preferred.
If be that the above glass fibre 111,112 of 15 μ m forms nonwovens 110 with fiber diameter, and multiple nonwovens 110 are carried out to the stacked core material 100 that forms, the fiber number of plies of core material 100 on thickness direction reduces, heat conduction path on thickness direction is shortened, and, when forming nonwovens 110, it is large that the emptying aperture diameter becomes.Therefore, owing to being subject to the impact of gas on thermal conductivity, 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.
If use the glass fibre 111,112 of length of staple more than 15mm, because length of staple is excessive with respect to fiber diameter, easily crooked so the rigidity of fiber reduces, and produce being interweaved between fiber, the area of contact between fiber is increased.Therefore, the heat conduction 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 formed by glass fibre 111,112 that vacuum heat insulation material of the present invention adopts with core material 100, preferably 30～600g/m
2.Grammes per square metre at nonwovens 110 is less than 30g/m
2situation under, because the aperture diameter of nonwovens 110 interior existence is large, so gas is large on the impact 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 while due to use glass fibre 111,112, manufacturing nonwovens 110 reduces, and the productivity reduction, so be not preferred.
So-called grammes per square metre generally refers to the unit of measurement of paper thickness, means the quality of the paper of every square metre, also referred to as the weight of every square metre.Unit as metering nonwovens 110 thickness is used grammes per square metre herein, and this nonwovens 110 consists of the glass fibre 111,112 that utilizes the manufacture of wet type copy paper method.
For example, in the record of Japanese Patent Publication communique JP No. 2006-17169 (patent documentation 2), the average diameter that preferably forms 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 finally obtained itself reduces.The diameter of the inorfil of formation 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 the wet type copy paper method to manufacture nonwovens, there is the shortcoming that dewatering efficiency reduces, productivity reduces.And in the present invention, about the adhering state between the fiber parameters such as the fiber diameter of inorfil, length of staple and fiber, as long as be used for improving the optimum condition of heat-shielding performance by selection, even adopt fiberglas chopped strand that fiber diameter the is larger example as inorfil, also can obtain heat-shielding performance far above the vacuum heat insulation material 1 of vacuum heat insulation material in the past.
In addition, even use fiber diameter to be less than the fiberglas chopped strand of 6 μ m, the increase rate of the vacuum heat insulation material heat-shielding performance finally obtained is compared with the situation of the fiberglas chopped strand that uses fiber diameter 10 μ m, also almost can ignore.Therefore, from productivity, price, aspect of performance, consider, the fiber diameter of fiberglas chopped strand is 6～15 μ m preferably.In the situation that use the glass fibre 111,112 of this scope, can obtain with suitable manufacture cost the heat-shielding performance ratio high vacuum heat insulation material 1 of vacuum heat insulation material in the past.
Use has the core material 100 of above-mentioned feature, utilizes known method can manufacture vacuum heat insulation material 1 of the present invention.Representative method is: in the structure of the vacuum heat insulation material 1 shown in Fig. 1, core material 100 is housed in and forms bag-shaped 200 inside of the outsourcing material with barrier properties for gases.The outsourcing material 200 of accommodating core material 100 under decompression state has high gas-obstructing character, and the protective layer that has hot sealing layer and protected for crack etc., can make for a long time the interior maintenance decompression state of outsourcing material 200.In addition, also can be used as outsourcing material 200 to multiple pellicular cascades with above-mentioned characteristic.
Example as outsourcing material 200 concrete structures can exemplify: make outermost surface be PETG (PET) resin, in the mesosphere use, have the ethylene-vinyl alcohol copolymer resin of aluminium-vapour deposition layer, the gas barrier film that innermost layer is the use high-density polyethylene resin; The gas barrier film that perhaps outermost surface is used nylon, mesosphere to use aluminium-vapour deposition PET resin and aluminium foil is two-layer, innermost layer is the use high-density polyethylene resin etc.
In addition, for the initial heat-shielding performance that keeps vacuum heat insulation material 1 with along with the heat-shielding performance of time history, preferably at the inner sorbents such as adsorbent, moisture adsorbent that use of vacuum heat insulation material 1.
Embodiment
Below several embodiments of the present invention are described, but the present invention is not limited thereto.
(embodiment 1～5, comparative example 1)
Be fiber diameter that the fiberglas chopped strand (being オ mono-ウ エ Application ス コ mono-ニ Application グ company (Owens Corning Corporation) manufactures) that 10 μ m, average fiber length are 10mm is put in water, the concentration that makes fiberglas chopped strand is 0.5 quality %, add the マ of the エ as the dispersing agent ノ mono-Application (Emanon of 1 mass parts with respect to the fiberglas chopped strand of 100 mass parts, TM trade mark) 3199 (Kao Corp's manufactures), by stirring the slip that has prepared fiberglas chopped strand.
The slip of the fiberglas chopped strand that use obtains utilizes the wet type copy paper method to be manufactured paper with pulp, and has prepared reticulated work.The suitably fluid binder of tackiness agent kind shown in dilution table 1 by the reticulated work impregnation that obtains therein, and the moisture that reticulated work is absorbed is adjusted, and makes nonwovens become the binder content shown in table 1.After this, by making the reticulated work drying, make the nonwovens 110 that vacuum heat insulation material adopts with core material 100.Grammes per square metre and the binder content of the nonwovens 110 obtained are as shown in table 1.
In addition, in table 1, in the tackiness agent kind of record, propylene liguid is acrylic emulsion (Dainippon Ink. & Chemicals Inc manufactures GM-4), and liquid PVA is the PVA aqueous solution (the Network ラ レ of Co., Ltd. is manufactured to PVA117 to be dissolved in warm water).
(comparative example 2～4)
The fiberglas chopped strand that adopts embodiment 1～5, comparative example 1 to use, utilize the slip that has prepared fiberglas chopped strand with embodiment 1～5, method that comparative example 1 is identical.
Granular PVA (ユ ニ チ カ Co., Ltd. manufactures OV-N) is added in water and stirred, and making its concentration is 10%, thereby has prepared granular binder slurry.
Add granular binder slurry in the fiberglas chopped strand slip obtained, so that the content of tackiness agent is as shown in table 1 with respect to nonwovens, use by being uniformly mixed the slip that obtains, utilizing the wet type copy paper method to be manufactured paper with pulp, prepared reticulated work.After this, by the reticulated work drying that makes to obtain, prepared the nonwovens 110 that vacuum heat insulation material adopts with core material 100.Grammes per square metre and the binder content of the nonwovens 110 obtained are as shown in table 1.
(example in the past)
As the core material that vacuum heat insulation material is used in the past, prepared the nonwovens as laminar fiber assembly, this laminar fiber assembly consists of the glass wool with the fiber diameter shown in table 1.
In addition, by the nonwovens 110 that vacuum heat insulation material is used with core material 100, at the temperature of 600 ℃, heat 30 minutes, remove organic principle, according to the following formula that utilizes of poor quality before and after heating, obtain the binder content shown in table 1.
Binder content (quality %)=[{ (quality before heating)-(quality after heating) }/(quality before heating)] * 100
10 nonwovens 110 of manufacturing by above embodiment 1～5, comparative example 1～4 are carried out stacked, make core material 100.Across separator, on the upper and lower surface of each core material 100 formed at the duplexer by obtaining, through-thickness applies 1kgf/cm respectively
2the pressure of (about 98kPa), in this state, the vacuum state that maintenance degree of vacuum is 0.01Torr (about 1.3Pa).In each core material 100 under this maintenance vacuum steady state, upper and lower surface temperature partly and the hot-fluid of each core material 100 of flowing through by measuring each core material 100 consisted of duplexer, calculate 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, mean the thermal conductivity of the nonwovens that formed by glass wool in the past in " thermal conductivity " hurdle of table 1.
Table 1
From the result shown in table 1, can find out, the thermal conductivity of the vacuum heat insulation material 1 of the embodiment of the present invention 1～5, and can the industrialization steady production below 0.85mW/mK.
In contrast, although 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, although can obtain the vacuum heat insulation material that thermal conductivity is 0.80mW/mK, but manufacturing the nonwovens operation with in operation nonwovens 110 is cut into the outsourcing material 200 consistent sizes of vacuum heat insulation material 1, the phenomenon that glass fibre 111,112 comes off in a large number from the surface of nonwovens 110 occurs, in addition, produce disconnected paper phenomenon during due to transmission between roller, so be difficult to stably be manufactured.In comparative example 4, although the vacuum heat insulation material 1 that can to obtain thermal conductivity be 0.60mW/mK, but the operation of removing tackiness agent needs the long period, in addition, in the operation of outsourcing material 200 inside that the core material 100 that consists of nonwovens 110 are sealing into to vacuum heat insulation material 1, easily make nonwovens 110 shapes at random, so be difficult to industrial mass production.In addition, the thermal conductivity of vacuum heat insulation material in the past is 1.70mW/mK.
Therefore, the vacuum heat insulation material of the application of the invention, can industrialization, vacuum heat insulation material that stably production heat-shielding performance is good, and the equipment such as refrigerator with good energy-efficient performance can be provided.
Above disclosed mode of execution and embodiment are illustration, and the present invention is not limited thereto.Scope of the present invention is not limited to the above-described embodiment and examples, but means by claim, and comprises content and all modifications carried out in the claim scope or the distortion be equal to claim.
Industrial applicibility
Vacuum heat insulation material of the present invention with core material and vacuum heat insulation material by least using many inorfils that utilize continuous filament method to manufacture, can make the thermal conductivity of core material reduce, and there is 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 (6)
1. a core material for vacuum heat insulation material (100), be laminated by multiple nonwovens (110), it is characterized in that,
Described nonwovens (110) comprises many inorfils (111,112) that utilize continuous filament method to manufacture, the fiber diameter of described inorfil (111,112) is more than 3 μ m, below 15 μ m, the average fiber length of described inorfil (111,112) is more than 3mm, below 15mm, and the straightness accuracy of described inorfil is very high
In described nonwovens (110), in the two-layer inorganic fibre mat of described nonwovens (110) inner stacks, form on most of inorfil (112) in described many inorfils of most of inorfil (111) in described many inorfils on upper strata and formation lower floor direction substantially parallel on the surface with described nonwovens (110) and extend, but not that mutual close-packed arrays is on parallel direction, but some contact between adjacent fiber, and in forming the Ge plane, the upper and lower of nonwovens towards the random direction dispersed arrangement
There is the fluid binder composition of relative volume in the skin section of described nonwovens (110), have the fluid binder composition of relatively small amount in the inside of described nonwovens (110).
2. core material (100) for vacuum heat insulation material according to claim 1, is characterized in that, the content of described adhesive ingredients with respect to described nonwovens (110) more than 0.1 quality %, below 1.5 quality %.
3. core material (100) for vacuum heat insulation material according to claim 1, is characterized in that, described inorfil (111,112) is glass fibre.
4. a vacuum heat insulation material (1) is characterized in that comprising:
Outsourcing material (200); And
Core material (100), be housed in the inside of described outsourcing material (200),
The within of described outsourcing material (200) remains in decompression state,
Described core material (100) at least comprises vacuum heat insulation material core material claimed in claim 1 more than.
5. the manufacture method of a core material for vacuum heat insulation material (100), for the manufacture method of vacuum heat insulation material claimed in claim 1 with core material, is characterized in that comprising the steps:
At least use many inorfils (111,112) and fluid binder, utilize the wet type copy paper method to manufacture the step of nonwovens (110), described many inorfils (111,112) utilize the continuous filament method manufacture, in described step, make to extend on most of inorfil (111,112) in described many inorfils direction substantially parallel on the surface of the described nonwovens (110) with manufacturing; And
The described nonwovens of polylith (110) is carried out to stacked step.
6. the manufacture method of a vacuum heat insulation material (1), be the manufacture method of vacuum heat insulation material claimed in claim 4, it is characterized in that comprising the steps:
At least use many inorfils (111,112) and fluid binder, utilize the wet type copy paper method to manufacture the step of nonwovens (110), described many inorfils (111,112) utilize the continuous filament method manufacture, in described step, make to extend on most of inorfil (111,112) in described many inorfils direction substantially parallel on the surface of the described nonwovens (110) with manufacturing;
Multiple described nonwovens (110) are carried out to stacked step; And
Multiple described nonwovens (110) after stacked are housed in to the inside of outsourcing material (200) and make the inside of described outsourcing material (200) remain in the step of decompression state.
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|---|---|---|---|
| JP2009-078086 | 2009-03-27 | ||
| JP2009078086A JP4772887B2 (en) | 2009-03-27 | 2009-03-27 | Core material for vacuum heat insulating material, vacuum heat insulating material, and manufacturing method thereof |
| PCT/JP2010/002155 WO2010109894A1 (en) | 2009-03-27 | 2010-03-26 | Core material for vacuum insulation material, vacuum insulation material, and processes for producing these |
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| CN102362115A CN102362115A (en) | 2012-02-22 |
| CN102362115B true CN102362115B (en) | 2013-12-18 |
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| JP (1) | JP4772887B2 (en) |
| CN (1) | CN102362115B (en) |
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| JP5736806B2 (en) * | 2011-02-01 | 2015-06-17 | 東芝ホームテクノ株式会社 | Vacuum insulation material and holder using the same |
| KR101525297B1 (en) * | 2013-01-16 | 2015-06-02 | (주)엘지하우시스 | Core material having glass wool for vacuum insulation, method for manufacturing the same and vacuum insulation using the same |
| 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 |
| 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 |
| 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 |
| 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 |
| JP7233070B2 (en) * | 2018-04-16 | 2023-03-06 | アクア株式会社 | vacuum insulation |
| CN108642706A (en) * | 2018-05-11 | 2018-10-12 | 上海邦季新材料有限公司 | A kind of preparation method of vacuum insulation panel glass fiber core material |
| DE102019201461A1 (en) * | 2019-02-05 | 2020-08-06 | Technische Universität Bergakademie Freiberg | Support core material for vacuum insulation panels |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN2033487U (en) * | 1988-08-04 | 1989-03-01 | 李芧华 | Vacuum chamber heat isolator of a refrigerator |
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| JPS61239100A (en) * | 1985-04-15 | 1986-10-24 | イビデン株式会社 | Acid resistant ceramic paper |
| JPH0489237A (en) * | 1990-08-01 | 1992-03-23 | Tokiwa Denki:Kk | Block constituted body |
| JP2003055889A (en) * | 2001-08-13 | 2003-02-26 | Nippon Synthetic Chem Ind Co Ltd:The | Binder for glass fiber nonwoven fabric |
| JP3490426B1 (en) * | 2002-05-31 | 2004-01-26 | 松下冷機株式会社 | Vacuum heat insulating material, and refrigeration equipment, cooling / heating equipment using the same, and vacuum heat insulating material core material and manufacturing method thereof |
| JP2004308691A (en) * | 2003-04-02 | 2004-11-04 | Nisshinbo Ind Inc | Vacuum heat insulating material and manufacturing method thereof |
| JP4438466B2 (en) * | 2004-03-18 | 2010-03-24 | 日本板硝子株式会社 | Vacuum heat insulating material and method for producing inorganic fiber sheet for vacuum heat insulating material |
| JP2006017169A (en) | 2004-06-30 | 2006-01-19 | Asahi Fiber Glass Co Ltd | Vacuum heat insulating material, core material for vacuum heat insulating material and its producing method |
| JP4713566B2 (en) * | 2007-12-28 | 2011-06-29 | シャープ株式会社 | Core material for vacuum heat insulating material, vacuum heat insulating material, and manufacturing method thereof |
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2009
- 2009-03-27 JP JP2009078086A patent/JP4772887B2/en not_active Expired - Fee Related
-
2010
- 2010-03-26 WO PCT/JP2010/002155 patent/WO2010109894A1/en active Application Filing
- 2010-03-26 CN CN201080013026.XA patent/CN102362115B/en not_active Expired - Fee Related
- 2010-03-26 DE DE112010001376T patent/DE112010001376T5/en not_active Ceased
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2033487U (en) * | 1988-08-04 | 1989-03-01 | 李芧华 | Vacuum chamber heat isolator of a refrigerator |
Non-Patent Citations (6)
| Title |
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| JP平4-89237A 1992.03.23 |
| JP昭61-239100A 1986.10.24 |
| JP特开2003-55889A 2003.02.26 |
| JP特开2004-308691A 2004.11.04 |
| JP特开2004-52774A 2004.02.19 |
| JP特开2005-265038A 2005.09.29 |
Also Published As
| Publication number | Publication date |
|---|---|
| DE112010001376T5 (en) | 2012-06-14 |
| WO2010109894A1 (en) | 2010-09-30 |
| CN102362115A (en) | 2012-02-22 |
| JP2010230082A (en) | 2010-10-14 |
| JP4772887B2 (en) | 2011-09-14 |
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