CN109477606A - Heat-insulating material and its manufacturing method - Google Patents
Heat-insulating material and its manufacturing method Download PDFInfo
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- CN109477606A CN109477606A CN201780042591.0A CN201780042591A CN109477606A CN 109477606 A CN109477606 A CN 109477606A CN 201780042591 A CN201780042591 A CN 201780042591A CN 109477606 A CN109477606 A CN 109477606A
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- gas
- layer
- heat
- sandwich layer
- insulating 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
- F16L59/02—Shape or form of insulating materials, with or without coverings integral with the insulating materials
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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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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Thermal Insulation (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a kind of heat-insulating material, has the sandwich layer (A) with fine hollow structure, is located at the outside of the sandwich layer (A) at least partially and can absorb the gas-absorbing layer (B) of gas and be located at the outside of the gas-absorbing layer (B) and can completely cut off the gas-insulated layer (C) of gas.
Description
Technical field
The present invention relates to heat-insulating material and its manufacturing methods.
Background technique
Heat-insulating material, as the heat-insulating material of refrigerator, reach in freezer, construction material etc., is used for improving heat-insulating property
The foaming bodies such as polyurethane foam.In recent years, it in order to further increase thermal insulation, uses to be connected to the polyurethane foam of hollow structure
Foam, glass fibre are core material, vacuum heat insulation materials (example made of these core materials are vacuum-packed with gas barrier packaging material
Such as referring to patent document 1, patent document 2).In addition, in order to manufacture such vacuum heat insulation materials, using vacuum chamber.
As the manufacturing method of the vacuum heat insulation materials without using vacuum chamber, propose in the foaming resin as core material
In composition after entrained gas absorbent, by being foamed using carbon dioxide gas, while being gone with gas absorbent
It removes to produce vacuum state, to improve the method for heat-insulating property (for example, with reference to patent document 3).
In addition to this, it is also proposed that be not in resin combination entrained gas absorbent but connection hollow structure
The gas absorbent of small bag-shaped is arranged to absorb the method for internal carbon dioxide (for example, with reference to special in the outside of polyurethane foam
Sharp document 4).
Existing technical literature
Patent document
Patent document 1: Japanese Laid-Open Patent Publication 7-234067 bulletin
Patent document 2: Japanese Laid-Open Patent Publication 9-138058 bulletin
Patent document 3: special open 1995-053769 bulletin
Patent document 4: special open 1999-334764 bulletin
Summary of the invention
Problems to be solved by the invention
But 10Pa high vacuum below is generally required in vacuum packaging in order to make it show high thermal insulation, even if
Vacuum degree slightly deteriorates, and performance can also drastically reduce.In addition, needing to maintain Gao Zhen for a long time using vacuum chamber in manufacturing process
Dummy status, this is the reason of productivity reduces.
In addition, in method previous described in patent document 3, it is difficult to the balance that adjustment foaming is absorbed with gas, Er Qie
Gas absorbent is added in core material can improve thermal conductivity, and therefore, it is difficult to realize sufficient thermal insulation.In addition, described in patent document 4
In method, gas absorption is local, therefore there is length the time required to removal gas, or the physics from connection hollow structure
The problems such as reduction of intensity.
Problem of the present invention is that providing the heat-insulating material with high thermal insulation without using vacuum chamber.
The solution to the problem
The inventors of the present invention further investigate the above subject, as a result, it has been found that by using having with fine hollow structure
Sandwich layer (A), at least partially positioned at the sandwich layer (A) outside and the gas-absorbing layer (B) of gas can be absorbed and be located at
The outside of the gas-absorbing layer (B) and the heat-insulating material of gas-insulated layer (C) that can completely cut off gas is able to solve the above subject.
That is, the present invention is as follows.
[1]
A kind of heat-insulating material, has:
Sandwich layer (A) with fine hollow structure,
At least part be located at the sandwich layer (A) outside and can absorb gas gas-absorbing layer (B) and
Positioned at the gas-absorbing layer (B) outside and the gas-insulated layer (C) of gas can be completely cut off.
[2]
The heat-insulating material according to [1], wherein the porosity of the sandwich layer (A) is in the range of 90~99%.
[3]
According to heat-insulating material described in [1] or [2], wherein being averaged for the fine hollow structure of the sandwich layer (A) is hollow straight
Diameter is in the range of 1~500 μm.
[4]
The heat-insulating material according to any one of [1]~[3], wherein the pressure of the fine hollow structure of the sandwich layer (A)
Power is in the range of 10~10000Pa.
[5]
The heat-insulating material according to any one of [1]~[4], wherein the thickness of the sandwich layer (A) is in 0.5~40mm
In the range of.
[6]
The heat-insulating material according to any one of [1]~[5], wherein the fine hollow structure of the sandwich layer (A) it is only
Vertical ducted body rate is 50% or more.
[7]
The heat-insulating material according to any one of [1]~[6], wherein the gas-absorbing layer (B) is directly or indirectly covered
Cover 40% or more of the surface the sandwich layer (A).
[8]
The heat-insulating material according to any one of [1]~[7], wherein the gas-absorbing layer (B), which can absorb, to be selected from
One or more of the group being made of carbon dioxide, vapor and oxygen.
[9]
[1] manufacturing method of heat-insulating material described in any one of~[8], has following processes:
Process (1) makes the resin expanded sandwich layer (A) for obtaining having fine hollow structure；And
Process (2) makes at least part be located at the outside of the sandwich layer (A) and can absorb the gas-absorbing layer (B) of gas
Absorb the internal gas of the sandwich layer (A).
[10]
The manufacturing method of the heat-insulating material according to [9], wherein obtain in the process of the sandwich layer (A), using extrusion
Foaming.
The effect of invention
In accordance with the invention it is possible to provide the heat-insulating material with high thermal insulation without using vacuum chamber.
Detailed description of the invention
Fig. 1 is a form of schematic diagram for showing the heat-insulating material using composite foam of the invention.
Fig. 2 is the schematic diagram for showing the other forms of the heat-insulating material using composite foam of the invention.
Specific embodiment
Hereinafter, mode for carrying out the present invention (hreinafter referred to as " present embodiment ") is described in detail.It is following
Present embodiment is for illustrating example of the invention, and purport does not limit the invention to the following embodiments and the accompanying drawings.The present invention can
Implemented with being deformed within the scope of its subject matter.
[heat-insulating material]
The heat-insulating material of present embodiment has: the sandwich layer (A) with fine hollow structure is (hereinafter, also referred to as " sandwich layer
(A)".), at least partially positioned at the sandwich layer (A) outside and can absorb gas gas-absorbing layer (B) (hereinafter, also referred to as
For " gas-absorbing layer (B) ".) and be located at the outside of the gas-absorbing layer (B) and the gas-insulated layer of gas can be completely cut off
(C) (hereinafter, also referred to as " gas-insulated layer (C) ".).Hereinafter, to sandwich layer (A), gas-absorbing layer (B) and gas-insulated
Layer (C) is described in detail.
[sandwich layer (A)]
In present embodiment described in example as shown in Figure 1, sandwich layer (A) is the core positioned at heat-insulating material center, and
And have using the bubble of microsize as the layer of the fine hollow space (hereinafter also referred to as " fine hollow structure ") of representative.
The sandwich layer (A) has fine hollow structure, therefore the heat-insulating property of the heat-insulating material in present embodiment greatly improves.
Fine hollow structure refers to that the average diameter of fine hollow structure is (hereinafter also referred to as " average in present embodiment
Hollow diameters ".) structure in 500 μm or less of range.
Average hollow diameters are preferably 1~300 μm, more preferably 1~100 μm, further preferably 1~50 μm.Pass through
Average hollow diameters are 500 μm hereinafter, there are thermal conductivitys when becoming decompression inside hollow body to be easily reduced, be easy to get it is good absolutely
The tendency of hot material.It on the other hand, is 1 μm or more by average hollow diameters, there are the tendencies that porosity is difficult to decrease.In order to
Average hollow diameters are obtained in the case where the fine hollow structure such as foaming body of above range, to the gas for facilitating foaming
Temperature and pressure, molding machine when the resin properties such as the type and amount of body and nucleating agent, the melt tension value of substrate resin, forming
Shape etc. optimize.The average hollow diameters of fine hollow structure can be surveyed by aftermentioned embodiment the method
It is fixed.
The porosity of sandwich layer (A) with fine hollow structure is preferably 90.0~99.0%, more preferably 93.0~
98.5%, further preferably 95.0%~98.0%.The thermal conductivity of base material part is high, therefore exists by making it in the range
And the tendency of thermal conductivity and intensity preferred scope can be made.Porosity such as is sent out in the sandwich layer (A) of above range in order to obtain
In the case where foam, increase the amount for facilitating the gas of foaming.The porosity of sandwich layer (A) can pass through aftermentioned embodiment institute
The method of stating is measured.
In order to show practical intensity and heat-insulating property, the independent ducted body rate of fine hollow structure is (in this specification
Independent ducted body rate refers in fine hollow structure all in sandwich layer (A) that not being connected to outside for sandwich layer (A) is fine hollow
The ratio of structure.) it is preferably 50% or more, more preferably 70% or more, further preferably 80% or more.Fine hollow structure
Independent ducted body rate can be measured by aftermentioned embodiment the method.
Sandwich layer (A) with fine hollow structure improves heat-insulating property by reducing the pressure of hollow space.
The pressure of fine hollow structure is preferably 10~10000Pa, more preferably 15~5000Pa, further preferably 20~
1000Pa.It is 10Pa or more by pressure, there are the influences of gas leakage etc. to become smaller relatively, it is able to maintain that the tendency of the pressure,
It is 10000Pa hereinafter, the low well insulated material of thermal conductivity can be easy to get by pressure.Pressure is in above-mentioned model in order to obtain
The fine hollow structure enclosed, for example, by using have can in a large amount of absorbent core layers (A) ability of contained gas gas-absorbing layer
(B).The pressure of fine hollow structure can be measured by aftermentioned embodiment the method.
The thickness of sandwich layer (A) with fine hollow structure is preferably 0.5~40mm, more preferably 1~25mm, further
Preferably 2~20mm.By being able to maintain that the heat-insulating property as heat-insulating material with a thickness of 0.5mm or more, by with a thickness of
40mm is become easy hereinafter, existing using gas-absorbing layer (B) absorbent core layer (A) internal gas, the excellent tendency of heat-insulating property.
The preparation method of sandwich layer (A) with fine hollow structure is not particularly limited, such as can enumerate and make in substrate
Containing foaming agent, by foaming fine hollow structure is produced, or makes hollow microcapsule etc. and be dispersed in substrate, or makes substrate
Method etc. containing the fibrous material with hollow structure.Wherein, it is contemplated that ease of manufacturing, gas permeability preferably make substrate
In contain foaming agent, the method that fine hollow structure is produced by extrusion foaming process, bead foam method, more preferable extrusion foaming
Method.
The resin used as substrate is not particularly limited, for example, can enumerate polyurethane, polyvinyl chloride, polycarbonate,
Polystyrene, polytetrafluoroethylene (PTFE), polyolefin, ionomer, polysulfones, cellulose acetate and the like, ethyl cellulose, poly- diformazan
Radical siloxane, organic siliconresin and chlorosulfonated polyethylene.From the angle of gas permeability and intensity, preferred polyurethane, polyvinyl chloride, poly-
Carbonic ester, polystyrene, polyolefin, cellulose acetate and the like and organic siliconresin, more preferable polystyrene and polyene
Hydrocarbon.One or more of these substances can be applied in combination.In addition, the commercially available product of these substances is readily available, it can be preferred
Use these substances.
Foaming agent manufactures fine hollow structure as the expansion such as the rubber of substrate or plastics for making, and is mainly roughly divided into
Chemical foaming agent and physical blowing agent.
Chemical foaming agent is to generate nitrogen, ammonia, hydrogen, carbon dioxide, vapor, oxygen by thermally decomposing or chemically reacting
The substance of the gases such as gas.
As chemical foaming agent, such as azo, nitrous base class, hydrazides, amino ureas, nitrine class, three can be enumerated
Azole, four azoles, combination, the mistake of isocyanates, heavy carbonate, carbonate, nitrite, hydride, sodium bicarbonate and acid
The combination of hydrogen oxide and saccharomycete and the combination of metal powder and acid generate the carbonate and heavy carbonate energy of carbon dioxide
The enough gas of generation high-purity, therefore it is preferred that.One or more of these substances can be applied in combination.In addition, these substances is commercially available
Product be readily available it is preferable to use.
Physical blowing agent is the substance for the physical changes such as bleeding off pressure, gasifying and foam by compressed gas.As specific
Example can enumerate the non-active gas such as nitrogen, aliphatic hydrocarbon, halogenated aliphatic hydrocarbon, water, carbon dioxide, from safety and ring
The angle that border adaptability, gas absorb, preferably carbon dioxide and water.One or more of these substances can be applied in combination.Separately
Outside, the commercially available product of these substances be readily available it is preferable to use.
About the additive amount of foaming agent, according to the difference of substrate type and foaming agent type, optimised quantity is different, therefore not
It can lump together.
Although use foaming agent fine hollow structure preparation method be by the substrate containing foaming agent into
Row foams to carry out, but foaming method is depending on the type of foaming agent and amount.As an example, using carbon dioxide
When gas is as physical blowing agent, as well known method, it can come according to method described in special open 2010-173263 preferred real
It applies.
[gas-absorbing layer (B)]
In present embodiment described in example as shown in Figure 1, gas-absorbing layer (B) is the sandwich layer positioned at heat-insulating material
(A) outside, and the layer of the gas in the sandwich layer (A) used when preparing the fine hollow structure can be absorbed.In addition, though
Gas-absorbing layer (B) has completely included sandwich layer (A) in example shown in Fig. 1, but since gas-absorbing layer (B) is located at sandwich layer (A)
Outside, therefore described in another example as shown in Figure 2, gas-absorbing layer (B) or do not include sandwich layer (A)
A part, comprising sandwich layer (A) end other than part form.Since gas-absorbing layer (B) absorbs gas, sandwich layer (A)
Hollow space pressure decline, therefore heat-insulating property improve.
Gas-absorbing layer (B) is the layer that gas can be for example absorbed and containing gas absorbent.As containing gas
The mode of absorbent can specifically be enumerated individually using the layer of gas absorbent or in the substrate containing gas absorbent
Layer.It, can also it is preferable to use natural rubbers, fourth two other than substrate identical with substrate used in sandwich layer (A) as substrate
The rubbers such as alkene rubber, silicon rubber, the bonding agents such as vinyl acetate emulsion bonding agent, rubber series bonding agents, starch-series bonding agent,
Adhesive.
Gas absorbent is the substance that can absorb gas, and the type of the gas of absorption is not particularly limited, such as can be with
Illustrate carbon dioxide, vapor, oxygen.
As gas absorbent, such as the hydroxide of alkali metal, the hydroxide of alkaline-earth metal, amine compounds can be enumerated
Object, epoxide, alkali metal, alkaline-earth metal, the hydride of alkali metal, the hydride of alkaline-earth metal, lithium aluminium hydride reduction, metal
Sulfate, calcium chloride, activated alumina, silica gel, molecular sieve, the carbonate of alkali metal, calcium oxide, sulfuric acid, phosphorous oxide, iron, Asia
The gold of sulfate, ascorbic acid, glycerol, MXD6 nylon, ethylenically unsaturated hydrocarbons, the polymer with cyclohexenyl group, titanium and cerium etc.
Belong to oxide oxygen atom defect sturcture body, the hydroxide of alkali metal, the hydroxide of alkaline-earth metal, metal sulfate,
Calcium chloride, activated alumina, silica gel, molecular sieve, the carbonate of alkali metal, calcium oxide, iron and sulphite it is cheap and
It is nearly free from non-active gas when absorbing gas, therefore it is preferred that.One or more of these substances can be applied in combination.In addition,
The commercially available product of these substances be readily available it is preferable to use.
When as gas-absorbing layer (B) using layer containing gas absorbent in the substrate, the additive amount of gas absorbent
It is preferably the range of 5~99 mass parts relative to 100 mass parts of substrate, in order to improve the uptake and speed of gas, more preferably
For 10~99 mass parts.
Gas-absorbing layer (B) both can may be single layer structure for multilayered structure, can be in gas-absorbing layer (B) and core
Setting absorbs the layer other than the layer of gas between layer (A).
As gas absorb other than layer, such as can enumerate bonding sandwich layer (A) and gas-absorbing layer (B) adhesive layer,
Prevent the ingredient of gas-absorbing layer from moving to the buffer layer of sandwich layer (A).
In order to improve the speed that gas-absorbing layer (B) absorbs the internal gas of removal sandwich layer (A), preferably gas-absorbing layer
(B) 40% or more of sandwich layer (A) surface area, more preferably 75% or more covering are directly or indirectly covered, is further preferably covered
80% or more.
The thickness of gas-absorbing layer (B) is preferably 10~500 μm, can take into account gas suction by the range, existing
Receive the tendency of performance and heat-insulating property.By being easy to get useful gas absorbent performance, passing through thickness with a thickness of 10 μm or more
Degree, hereinafter, there are gas-absorbing layer in heat-insulating material (B) proportion is not too big, is able to suppress thermal conductivity deterioration for 500 μm
Tendency.
Gas-absorbing layer (B) for example can by resin melting mixing gas absorbent prepare resin granular material, carry out
Film shapes to prepare.As other way, can also be by being kneaded gas absorbent in above-mentioned bonding agent after, be coated in sandwich layer
(A) it prepares or on film.
[gas-insulated layer (C)]
In present embodiment described in example as shown in Figure 1, gas-insulated layer (C) is positioned at gas-absorbing layer (B)
Outside and the layer that the gas from outside can be completely cut off.
For gas-insulated layer (C), it is not particularly limited as long as it can prevent the layer in air intrusion sandwich layer (A),
In the group formed with the evaporation film selected from evaporation film, Si oxide by metal oxide, metal deposition film, metallic film
The gas-insulated property of a kind or more of layered body is excellent, therefore it is preferred that.These can be obtained in the form of commercially available product, can preferably be made
With.One or more of these can be applied in combination.
Gas-insulated layer (C) can form multilayered structure or single layer structure, in addition gas-insulated layer (C) and gas-absorbing layer
(B) or between atmosphere, the layer other than the layer of isolation gas can be set.
As the layer other than the layer of isolation gas, such as sealing resin layer for being sealed can be enumerated, prevent gas
The protective layer of the pin hole of body isolation layer (C).
The thickness of gas-insulated layer (C) is preferably 1 μm~500 μm, by the range, exist can take into account it is gas-insulated
The tendency of performance and heat-insulating property.
[manufacturing method of heat-insulating material]
The manufacturing method of heat-insulating material about present embodiment, as long as it can obtain the heat-insulating material of present embodiment
It is not particularly limited, such as with following processes:
Process (1) makes the resin expanded sandwich layer (A) for obtaining having fine hollow structure；And
Process (2) allows to the gas for gas-absorbing layer (B) absorbent core layer (A) inside for absorbing gas.
The process (1) for obtaining sandwich layer is not particularly limited, and can enumerate identical with above-mentioned " preparation method of sandwich layer (A) "
Method.In addition, the process (2) for absorbing gas is not particularly limited, such as can be by the sandwich layer that makes to have fine hollow structure
(A) it is carried out with gas-absorbing layer (B) and gas isolation layer (C) Composite.As the method for Composite, such as can enumerate pre-
Conventional dry lamination bonding gas-absorbing layer (B) and gas-insulated layer (C) is first passed through, in the gas-absorbing layer (B) and gas
Coating adhesive carries out be bonded method etc. with sandwich layer (A) on the composite layer of isolation layer (C).As other way, can also arrange
It lifts and first passes through conventional dry lamination or heat lamination bonding sandwich layer (A) and gas-absorbing layer (B) in advance, covered with gas-insulated layer (C)
The sandwich layer (A) is covered with the complex of gas-absorbing layer (B) and without bonding method etc..In addition, excellent when using heat-insulating material
Choosing makes terminal part closure, such as by carrying out pressing using heat-sealing to carry out closure, can be realized thermal insulation and performance
Long term stabilization.
In the process (1) for obtaining sandwich layer, it is preferable to use extrusion foaming process in above-mentioned " preparation method of sandwich layer (A) ".
Embodiment
Hereinafter, present embodiment is specifically described by embodiment, but present embodiment is not by these embodiments
Any restrictions.
[the average hollow diameters of fine hollow structure]
The average hollow diameters of fine hollow structure calculate by the following method.Specifically, firstly, edge and thickness direction phase
Vertical any X-direction and Y-direction cutting sandwich layer (A) perpendicular with thickness direction and X-direction, it is micro- with scanning electron
The central portion of cross sections is amplified 20~100 times and shot by mirror (Japan Electronics trade name " JSM-6460LA ").
Then, by the image printing of shooting on A4 paper, the straight line of a long 60mm is drawn on the image.Herein, for along X
The section of direction cutting, draws straight line with X-direction in parallel, for the section cut along Y-direction, draws straight line in parallel with Y-direction.
According to the hollow quantity present on above-mentioned each straight line (including point contact), hollow mean chord is calculated using following formula
(t), the mean chord (direction tY) as the mean chord of X-direction (direction tX) and Y-direction.
Mean chord (t)=60 (mm)/(multiplying power of hollow quantity × photo)
In turn, in the enlarged photograph of the section cut in X direction and along the section cut with the perpendicular direction of Y-direction
In enlarged photograph the two, the straight line of a long 60mm parallel with Z-direction (thickness direction), the Z-direction and X-direction are drawn respectively
And Y-direction is perpendicular, counts hollow quantity present on these straight lines, calculates the mean chord of the thickness direction of cross sections
(t), the arithmetic mean of instantaneous value for calculating these mean chords (t), using the arithmetic mean of instantaneous value as the mean chord (side tZ of thickness direction
To).
Then, the mean chord (t) in all directions based on calculating calculates the flat of fine hollow structure by following formula
Equal hollow diameters.
Average hollow diameters (mm)=(direction the tX direction+tY direction+tZ)/3
[porosity]
According to the density of the density of the substrate on the basis as sandwich layer (A) and sandwich layer (A), sandwich layer is found out using following formulas
(A) porosity.
Porosity (%)=(density of matrix density-sandwich layer (A))/(density of substrate) × 100
[the independent ducted body rate of fine hollow structure]
The examination of heat-insulating material is cut out in a manner of becoming the rectangular-shape of long 25mm, width 25mm, thickness 20mm for sandwich layer (A)
Piece is tested (when thickness deficiency, the test film cut out to be laminated so that above-mentioned rectangular-shape is made.), then condition be atmospheric pressure under,
Test film is stood 1 day in relative humidity 50%, 23 DEG C of temperature of thermostatic chamber.
Then, the correct apparent bulking value Va of the test film is measured.Then, after abundant drying test piece, according to
Sequence C described in ASTM-D2856-70 measures body by the air comparison expression densimeter 930 of Toshiba's Beckman Co. Ltd. system
Product value Vx.Then, it is based on bulking value Va and bulking value Vx, the independent ducted body rate of fine hollow structure is calculated by following formula.
It should be noted that each measurement and each calculate are to carry out for 5 different test films, and find out its average value.This is put down
Mean value is as independent ducted body rate.
Independent ducted body rate (%)=(Vx-W/ ρ) × 100/ (Va-W/ ρ)
Vx: the hollow of independent hollow space in the volume and foamed resin products of the resin of fine hollow structure is constituted
The sum of total measurement (volume) (cm3)
Va: the apparent volume (cm that geometry calculates3)
W: the quality (g) of foamed resin products
ρ: the density (g/cm of the substrate of sandwich layer (A) is constituted3)
[pressure of fine hollow structure]
1 > of < method
The injection needle of the internal diameter 1.2mm of absolute pressure transducer (optex-fa company: FHAV-050KP) has been welded in preparation.
Then, the heat-insulating material of the injection needle with absolute pressure transducer and preparation is put into glove box, is replaced into two in glove box
Carbonoxide.Then, the tip of the injection needle with absolute pressure transducer is made to be pierced into the center of the sandwich layer (A) of the heat-insulating material of preparation
Portion is coated with epoxy bonding agent (Nichiban company: ARALDITE AR-R30) in the part of insertion injection needle, so that gas
It will not be externally entering.The pressure of fine hollow structure is measured after 7 days.It should be noted that being pierced into injection needle is to be insulated
Implement within 1 hour after material manufacture.It should be noted that the heat-insulating material for determining pressure can not measure behind it is aftermentioned
Thermal conductivity, therefore, thermal conductivity is measured by preparing other heat-insulating materials of identical composition.
2 > of < method
Integrated heat-insulating material is carried out not over bonding agent etc. and sandwich layer (A) for gas-insulated layer (C), using energy
Enough following methods being more simply measured measure.
Prepare the vacuum chamber of acrylic acid, high-precision vacuum meter (CANON ANELVA corporation: M- is installed wherein
342DG).Then, the displacement that distance after 2 weeks heat-insulating materials are put into chamber, will be critically measured after manufacture is passed
Sensor (Omron Corp's system: ZX2) is arranged outside chamber, so as to measure the displacement sensor and the heat insulating material for being put into chamber
Expect the distance on surface.Then, by the slow evacuation of chamber interior, the gas when the pressure of chamber interior is lower than the pressure of sandwich layer (A)
Body isolation layer (C) can move, therefore by sensing the movement with displacement sensor, measure the pressure of sandwich layer (A).
[thickness]
For the thickness of sandwich layer (A), vernier is used to measure sandwich layer (A) as unit of 0.1 millimeter.
For the thickness of gas-absorbing layer (B) and gas isolation layer (C), with scanning electron microscope (Japan Electronics system,
JSM-6460LA the section for) observing each layer is measured as unit of 1 micron.
The thickness of the test specimen of heat guard is measured while measuring thermal conductivity by above-mentioned HFM436.
[thermal conductivity]
According to HFM method described in JIS A1412, the thermal conductivity measurement device HFM436 made using NETZSCH Japan (strain)
The thermal conductivity of heat-insulating material is measured at 25 degrees c.
Thermal conductivity is
0.020W/mK is below to be evaluated as A,
0.021~0.025W/mK's is evaluated as B,
0.026~0.030W/mK's is evaluated as C,
0.031W/mK's or more is evaluated as D.
It is unqualified to be evaluated as being considered as D.
[embodiment 1]
The preparation of < gas-absorbing layer (B1) and Composite > with gas-insulated layer (C)
Substrate is used as using polyvinyl resin (Dow Chemical ELITE5220G), calcium hydroxide is as carbon dioxide
Absorbent and calcium oxide are prepared gas-absorbing layer (B1) as water vapor absorption agent.
Firstly, carrying out melting mixing, preparation with polyvinyl resin/calcium hydroxide=51 mass parts/49 mass parts ratio
The resin granular material (b1-1) of gas-absorbing layer (B) formation.Similarly, with polyvinyl resin/calcium oxide=60 mass parts/40 matter
The ratio for measuring part carries out melting mixing, prepares the resin granular material (b1-2) of gas-absorbing layer (B) formation.
Then, duplicature forming is carried out with the ratio of 1:1 using the resin granular material (b1-1) and (b1-2), obtains 100 μ of thickness
The gas-absorbing layer (B1) of m.
It then, will be eastern using bar coater coating ethyl acetate in (b1-1) the layer side of the gas-absorbing layer of preparation (B1)
Foreign Morton corporation dry lamination is diluted to 2 times of obtained coating fluids with bonding agent TM250HV and curing agent CAT-RT86L-60
And after drying, the layer knot with PET/DL/Al/LDPE/LLDPE as gas-insulated layer (C) is bonded to by dry lamination
Commercially available gas barrier film (the Sun of structure
A.Kaken: retort pouch is used, PET: polyethylene terephthalate, DL: bonding agent, Al: aluminium foil, LDPE: low close
Spend polyethylene, LLDPE: straight-chain short-chain branch polyethylene) the side LLDPE carry out Composite, obtain by gas-absorbing layer (B1) and
The multilayer film of gas-insulated layer (C) composition.
The preparation of < sandwich layer (A1) and Composite > with multilayer film
Prepare the tandem type extruder that the first extruder and the second extruder are formed by connecting.By the polyphenyl second of 100 mass parts
Olefine resin (PS Japan corporation G9305) supplies to the first extruder of the tandem type extruder and carries out melting mixing, from the
The midway of the flow path of one extruder is pressed into the carbon dioxide as foaming agent, by the polystyrene resin and titanium dioxide of molten condition
Polystyrene resin is continuously fed into the second extruder on this basis and carries out melting mixing by carbon equably mixed milling, and
And it is cooled to the temperature for being suitble to foaming.Then, ring mould of the self installation in the second extruder front end squeezes polystyrene resin
It foams out, obtained cylindric foam molding is cooled down close to plug, in any of plug, will be justified with cutter
The foam molding of tubular is cut, and obtains the sandwich layer (A1) of the thick 5mm with fine hollow structure.Being averaged for sandwich layer (A1) is hollow
Diameter, porosity, independent ducted body rate are as described in table 1.
Then, in the gas of the multilayer film with gas-absorbing layer (B1) and gas isolation layer (C) of above method preparation
(b1-2) the layer side of absorbed layer (B1), using with the method identical method bonding agent tack core of Nian Jie gas-insulated layer (C)
Layer (A).Then, with heat sealing machine (FUJIIMPULSE corporation) with the range of wide 20mm by terminal part closure.It is measured after 7 days
The thermal conductivity and pressure (method of the sandwich layer (A1)-gas-absorbing layer (B1)-gas-insulated layer (C) complex (heat-insulating material)
1).Show the result in table 1.
[embodiment 2]
The preparation > of < gas-absorbing layer (B2)
Substrate is used as using polyvinyl resin (Dow Chemical ELITE5220G), calcium hydroxide is as carbon dioxide
Absorbent and calcium oxide are as water vapor absorption agent preparation gas-absorbing layer (B2).
Firstly, carrying out melting mixing, preparation with polyvinyl resin/calcium hydroxide=50 mass parts/50 mass parts ratio
The resin granular material (b2-1) of gas-absorbing layer (B) formation.Similarly, with polyvinyl resin/calcium oxide=50 mass parts/50 matter
The ratio for measuring part carries out melting mixing, prepares the resin granular material (b2-2) of gas-absorbing layer (B) formation.
Then, duplicature forming is carried out with the ratio of 1.4:1 using the resin granular material (b2-1) and (b2-2), obtains thickness
120 μm of gas-absorbing layer (B2).
The preparation of < sandwich layer (A2) and Composite > with gas-absorbing layer (B2)
Using carbon dioxide and water as foaming agent, in addition to this, sandwich layer is prepared using method same as Example 1
(A).The average hollow diameters of the sandwich layer (A2) of preparation, porosity, independent ducted body rate are as described in table 1.
Then, it prepared by (b2-1) layer side bonds of the sandwich layer (A2) of above method preparation and gas-absorbing layer (B2) compound
Body.The process carries out under carbon dioxide atmosphere.
The complex of < sandwich layer (A2) gas-absorbing layer (B2) and the Composite > of gas-insulated layer (C)
The sandwich layer (A2) and gas-absorbing layer (B2) of above-mentioned preparation is completely covered in the gas-insulated layer (C) described in embodiment 1
Complex, after the gas as far as possible between removal complex and gas-insulated layer (C), with heat sealing machine with the range of wide 10mm general
Terminal part closure.The process carries out under carbon dioxide atmosphere.The sandwich layer (A2)-gas-absorbing layer (B2)-is measured after two weeks
The thermal conductivity and pressure (method 2) of the complex (heat-insulating material) of gas-insulated layer (C).Show the result in table 1.
[embodiment 3]
As sandwich layer (A) using the average hollow diameters with table 1, the sandwich layer (A3) of porosity, independent ducted body rate, remove
It other than this, is prepared complex (heat-insulating material) using method same as Example 2, measures thermal conductivity and pressure (method 2).It will
As a result shown in table 1.
[embodiment 4]
Sandwich layer (A2) is obtained using method same as Example 2.Then, the 1/3 of the surface sandwich layer (A2) is inhaled with gas
Layer (B2) bonding is received, carries out whole covering with gas-insulated layer (C) from thereon.It is being removed between gas-insulated layer (C) as far as possible
After gas, with heat sealing machine with the range of wide 10mm by terminal part closure.The process carries out under carbon dioxide atmosphere.After two weeks
Measure the thermal conductivity and pressure of the sandwich layer (A2)-gas-absorbing layer (B2)-gas-insulated layer (C) complex (heat-insulating material)
(method 2).Show the result in table 1.
[comparative example 1]
Using the ProductName sell board of the previous storehouse foamed polystyrene Ti Jiyan chemical industrial company as exhausted
Hot material measures thermal conductivity, and result is poorer than embodiment (table 1).The result of other measurements and evaluation is shown in table 1.
[comparative example 2]
Without using gas-absorbing layer (B1) and gas isolation layer (C), only it is prepared by method same as Example 1 and obtains
Sandwich layer (A1), it is thermally conductive as Thermal insulation measurement thermal conductivity, but since the pressure of fine ducted body does not reduce
The result of rate is poorer than embodiment (table 1).The result of other measurements and evaluation is shown in table 1.
[comparative example 3]
Without using gas-absorbing layer (B2) and gas isolation layer (C), only it is prepared by method same as Example 2 and obtains
Sandwich layer (A2), it is thermally conductive as Thermal insulation measurement thermal conductivity, but since the pressure of fine ducted body does not reduce
The result of rate is poorer than embodiment (table 1).The result of other measurements and evaluation is shown in table 1.
[reference example 1]
The powder of the calcium hydroxide and calcium oxide that use when the gas-absorbing layer pellet that will prepare embodiment 1, which is put into, to be had
Gas is prepared in the pouch of gas permeability absorbs pouch.It then, will after obtaining sandwich layer (A1) by method same as Example 1
Gas absorbs pouch and is placed on sandwich layer (A1).Pouch is absorbed to sandwich layer (A1) and gas with gas-insulated layer (C) integrally to have carried out
All standing, it is with the range of wide 10mm that terminal part is closed with heat sealing machine after removing the gas between gas-insulated layer (C) as far as possible
Change.The process carries out under carbon dioxide atmosphere.The pressure (method 2) and thermal conductivity of the complex are measured after two weeks.But by
In absorbing pouch rather than gas-absorbing layer (B) using bag-shaped gas, therefore pressure reduction very little.In addition, due to small
Bag portion point is outstanding from the surface of heat-insulating material, therefore could not Accurate Determining thermal conductivity.
[table 1]
Japanese patent application (the Patent 2016-136563 that the application is submitted based on July 11st, 2016 to Japanese Patent Office
Number), content is incorporated by reference as the application.
Claims (10)
1. a kind of heat-insulating material, has:
Sandwich layer (A) with fine hollow structure,
At least part be located at the sandwich layer (A) outside and can absorb gas gas-absorbing layer (B) and
Positioned at the gas-absorbing layer (B) outside and the gas-insulated layer (C) of gas can be completely cut off.
2. heat-insulating material according to claim 1, wherein the porosity of the sandwich layer (A) is in the range of 90~99%.
3. heat-insulating material according to claim 1 or 2, wherein being averaged for the fine hollow structure of the sandwich layer (A) is hollow
Diameter is in the range of 1~500 μm.
4. heat-insulating material described in any one of claim 1 to 3, wherein the fine hollow structure of the sandwich layer (A)
Pressure is in the range of 10~10000Pa.
5. heat-insulating material according to any one of claims 1 to 4, wherein the thickness of the sandwich layer (A) 0.5~
In the range of 40mm.
6. heat-insulating material according to any one of claims 1 to 5, wherein the fine hollow structure of the sandwich layer (A)
Independent ducted body rate is 50% or more.
7. heat-insulating material described according to claim 1~any one of 6, wherein the gas-absorbing layer (B) is direct or indirect
Cover 40% or more of the surface the sandwich layer (A).
8. heat-insulating material according to any one of claims 1 to 7, wherein the gas-absorbing layer (B) can absorb choosing
One or more of free carbon dioxide, vapor and group of oxygen composition.
9. the manufacturing method of heat-insulating material according to any one of claims 1 to 8 has following processes:
Process (1) makes the resin expanded sandwich layer (A) for obtaining having fine hollow structure；And
Process (2) makes at least part be located at the outside of the sandwich layer (A) and can absorb gas-absorbing layer (B) absorption of gas
The internal gas of the sandwich layer (A).
10. the manufacturing method of heat-insulating material according to claim 9, wherein obtain adopting in the process of the sandwich layer (A)
Use extrusion foaming process.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016136563 | 2016-07-11 | ||
| JP2016-136563 | 2016-07-11 | ||
| PCT/JP2017/024835 WO2018012402A1 (en) | 2016-07-11 | 2017-07-06 | Heat insulating material and method for producing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109477606A true CN109477606A (en) | 2019-03-15 |
Family
ID=60952482
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201780042591.0A Pending CN109477606A (en) | 2016-07-11 | 2017-07-06 | Heat-insulating material and its manufacturing method |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP7192497B2 (en) |
| KR (1) | KR20190027854A (en) |
| CN (1) | CN109477606A (en) |
| TW (1) | TW201821727A (en) |
| WO (1) | WO2018012402A1 (en) |
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- 2017-07-06 WO PCT/JP2017/024835 patent/WO2018012402A1/en active Application Filing
- 2017-07-06 KR KR1020197003447A patent/KR20190027854A/en not_active Application Discontinuation
- 2017-07-06 CN CN201780042591.0A patent/CN109477606A/en active Pending
- 2017-07-06 JP JP2018527564A patent/JP7192497B2/en active Active
- 2017-07-11 TW TW106123225A patent/TW201821727A/en unknown
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2018012402A1 (en) | 2018-01-18 |
| JPWO2018012402A1 (en) | 2019-05-09 |
| TW201821727A (en) | 2018-06-16 |
| KR20190027854A (en) | 2019-03-15 |
| JP7192497B2 (en) | 2022-12-20 |
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