CN1254367C - Laminated membrane laminated aluminium plate and its mfg. method - Google Patents
Laminated membrane laminated aluminium plate and its mfg. method Download PDFInfo
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- CN1254367C CN1254367C CNB021087687A CN02108768A CN1254367C CN 1254367 C CN1254367 C CN 1254367C CN B021087687 A CNB021087687 A CN B021087687A CN 02108768 A CN02108768 A CN 02108768A CN 1254367 C CN1254367 C CN 1254367C
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- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000001398 aluminium Chemical class 0.000 title claims description 90
- 239000012528 membrane Substances 0.000 title claims description 88
- 229920005989 resin Polymers 0.000 claims abstract description 524
- 239000011347 resin Substances 0.000 claims abstract description 524
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 95
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000049 pigment Substances 0.000 claims abstract description 59
- 239000011159 matrix material Substances 0.000 claims abstract description 41
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims abstract description 21
- 239000004411 aluminium Substances 0.000 claims description 85
- 238000004040 coloring Methods 0.000 claims description 56
- 238000010438 heat treatment Methods 0.000 claims description 26
- 238000001125 extrusion Methods 0.000 claims description 10
- 229920001225 polyester resin Polymers 0.000 claims description 10
- 238000012545 processing Methods 0.000 abstract description 20
- 238000000465 moulding Methods 0.000 abstract description 15
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 2
- 238000002845 discoloration Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 138
- 230000006978 adaptation Effects 0.000 description 26
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 229920002302 Nylon 6,6 Polymers 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 238000007493 shaping process Methods 0.000 description 16
- 229920002292 Nylon 6 Polymers 0.000 description 14
- 239000004408 titanium dioxide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000004453 electron probe microanalysis Methods 0.000 description 5
- 230000001788 irregular Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
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- 229910052719 titanium Inorganic materials 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 238000012800 visualization Methods 0.000 description 3
- 229920000571 Nylon 11 Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002040 relaxant effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000952 Be alloy Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 description 1
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000003678 scratch resistant effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
- B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/24—Aluminium
Landscapes
- Laminated Bodies (AREA)
Abstract
The invention provides a laminated film laminated aluminum panel not generating peeling between resin layers or between a resin and an aluminum panel and capable of suppressing the discoloration of a processed part even if receiving severe molding processing by integrally forming the interface between resin layers in the aluminum panel having a plurality of resin layers laminated there on and dispersing the color pigment introduced into the resin layers so as to form a predetermined continuous concentration distribution across the resin layers, and a method for manufacturing the same. In the laminated film laminated aluminum panel M1 wherein two or three resin layers 1, 2 and 3 are laminated on the single surface or both surfaces of the aluminum panel A containing aluminum as a main component, the matrix resins constituting the respective resin layers 1, 2 and 3 are resins having compatibility and these resin layers 1, 2 and 3 are heat-treated within a temperature range from the melting points of the resin layers to the decomposition points of them.
Description
Technical field
The present invention relates to the laminated membrane laminated aluminium plate and the manufacture method thereof of the stacked resin of integrally formed a plurality of resin boundary surfaces on aluminium sheet.Laminated membrane laminated aluminium plate of the present invention is specially adapted to electronic-component containers such as capacitor case.
Background technology
In the past, the shaping of the metallic plate thin-walled material being carried out strictnesses such as deep-draw processing or attenuate stretch process processed having in the round-ended cylinder shape container of shape, used the stacked laminated resin material of thermoplastic resin on above-mentioned thin-walled material.The following material of general use in this laminated resin material, be and give required outward appearance and have round-ended cylinder shape container to print above-mentioned, for the color of hidden metallic plate as this printed substrates, the stacked material that contains based on the resin molding of the various pigment of white on metallic plate.
As such laminated resin material, for example as shown in Figure 7, open the spy and to have proposed the pigmented polyester covered metal plate 40 that the stacked a plurality of polyester based resin films 10,20 that contain pigment form on metallic plate 30 in the flat 11-348218 communique.
In addition, a kind of round-ended cylinder shape packing container that has is proposed in the Te Kaiping 4-3411 communique, promptly the both sides that are layered in the colored polyamide resin bed that contains colouring agent on face of aluminium sheet are provided with the composite polyamide resin bed of the three-decker that the transparent polyamide resin bed do not contain colouring agent forms, the plywood of while stacked carboxyl acid modified polyolefin resin layer on another side, carry out deep-draw processing, make the composite polyamide resin bed be the outside form round-ended cylinder shape packing container arranged.
Yet stacked in the laminated resin material of these a plurality of resins, the interface between each resin bed is clearly demarcated, adds man-hour being subjected to very harsh shaping, the problem of peeling off between each resin bed occurs because of situation is different.In addition, sneak into the coloring pigment in the given resin bed of above-mentioned laminated resin material, be subjected to very harsh shaping at above-mentioned laminated resin material and add man-hour, its resin layer thickness that adds the Ministry of worker becomes than original thin thickness, therefore the absolute magnitude owing to the coloring pigment of sneaking into reduces, so there is the problem that adds Ministry of worker's change color.
Summary of the invention
In order to address the above problem, first problem of the present invention is to provide a kind of laminated membrane laminated aluminium plate and manufacture method thereof, promptly stacked in the laminated membrane laminated aluminium plate of a plurality of resin beds, by making the integrated formation in interface between these resin beds, even carry out strict shaping processing, also can not produce the laminated membrane laminated aluminium plate of peeling off between resin bed or between resin and aluminium sheet.
In addition, in order to address the above problem, second problem of the present invention is to provide a kind of laminated membrane laminated aluminium plate and manufacture method thereof, promptly stacked in the laminated membrane laminated aluminium plate of a plurality of resin beds, by being passed between each resin bed, disperses the coloring pigment of sneaking into given resin bed with given continuous CONCENTRATION DISTRIBUTION, even carry out strict shaping processing, also can suppress to add the laminated membrane laminated aluminium plate of Ministry of worker's variable color.
In order to achieve the above object, the inventor etc. further investigate, found that: at first stacked in the laminated membrane laminated aluminium plate of a plurality of different resins, by under these temperature more than melting point resin and below the decomposition point, heating, can make the interface between each resin bed form one, even the result adds man-hour implementing harsh shaping, also can suppress between resin bed as far as possible or resin and aluminium sheet between produce peel off.In addition, also find: disperse with given continuous CONCENTRATION DISTRIBUTION because the coloring pigment of sneaking in the given resin bed is passed between each resin bed, even thereby implement strict shaping processing and also can suppress to add Ministry of worker's variable color.So, finished the present invention based on these technological thoughts.
That is to say, laminated membrane laminated aluminium plate of the present invention, it is the laminated membrane laminated aluminium plate that on a face of aluminium sheet that with aluminium main component, is laminated to few two layers of resin layer at least, the matrix resin that constitutes above-mentioned each resin bed is the resin with intermiscibility, at least in one deck of above-mentioned resin bed, sneak into coloring pigment, constitute more than the fusing point of matrix resin of above-mentioned each resin bed and the stacked above-mentioned resin bed of heat treatment under the temperature below the decomposition point at all.
In other words, laminated membrane laminated aluminium plate of the present invention, it is the laminated membrane laminated aluminium plate that on a face of aluminium sheet that with aluminium main component, is laminated to few two layers of resin layer at least, the matrix resin that constitutes above-mentioned each resin bed is the resin with intermiscibility, at least in one deck of above-mentioned resin bed, sneak into coloring pigment, above-mentioned matrix resin each interface between above-mentioned resin bed is completely become one mutually to each resin bed diffusion.
Constitute in this way, make the interface integrated by the resin mutual diffusion between resin bed that makes above-mentioned laminated membrane laminated aluminium plate, can make the laminated membrane laminated aluminium plate with following characteristic: the stripping performance between each resin bed that the difference of all characteristics that have because of each resin bed causes obtains relaxing, in addition, the internal stress of processing the resin bed that produces because of being shaped also can obtain relaxing, and the reduction of the adaptation between adaptation between resin bed and resin bed and aluminium sheet can be inhibited.And, constitute in this way, owing to needn't in all above-mentioned two layers or three-layer resin layers, add coloring pigment, thereby can make the laminated membrane laminated aluminium plate of having simplified manufacturing process.
The term that uses among the present invention " decomposition point " is meant, as hereinafter describing in detail, when forming laminated membrane laminated aluminium plate of the present invention, the matrix resin that constitutes each resin bed of stacked film is kept and the upper limit of the temperature range of the corresponding required rerum natura of its purpose purposes.
And, in laminated membrane laminated aluminium plate of the present invention, the coloring pigment of sneaking in the above-mentioned resin bed is passed between above-mentioned each resin bed disperse with given continuous CONCENTRATION DISTRIBUTION.
Constitute in this way, owing to coloring pigment disperses with continuous CONCENTRATION DISTRIBUTION between above-mentioned each resin bed, so can make a kind of laminated membrane laminated aluminium plate that has suppressed to add the irregular colour that the resin layer thickness variation occurs in man-hour owing to being shaped.
And in the laminated membrane laminated aluminium plate of the present invention, above-mentioned resin bed constitutes by three layers at least, and in above-mentioned three layers, the CONCENTRATION DISTRIBUTION of the coloring pigment in intermediate layer is the highest.
Constitute in this way, carry out because the diffusion of coloring pigment is the resin bed of resin bed to the upper and lower from above-mentioned intermediate layer, thus can make coloring pigment disperse the laminated membrane laminated aluminium plate of homogeneous more.
In laminated membrane laminated aluminium plate of the present invention, can making in the above-mentioned resin bed at least, one deck is polyester based resin or polyamide-based resin.
Constitute in this way and since in the above-mentioned resin bed at least one deck constitute by polyester based resin or polyamide-based resin, so can make insulating properties and all good laminated membrane laminated aluminium plate of shaping processability.In addition, be applicable to polyester based resin of the present invention and polyamide-based resin be this area in the past known, obtain and cheap material easily.In addition, because the various rerum naturas of these resins are clear and definite, so the conditioned disjunction when determining to make laminated membrane laminated aluminium plate of the present invention easily carries out quality management.
In addition, the manufacture method of laminated membrane laminated aluminium plate of the present invention is made up of following operation:
With adopt will have mutually on one side intermiscibility and by at least two kinds of matrix resins that different resins is formed be squeezed into simultaneously membranaceous one side carry out stacked film that stacked co-extrusion pressure method makes cover at least one face of aluminium sheet operation and
In heat treated operation more than the fusing point of all above-mentioned matrix resins and under the temperature below the decomposition point.
Adopt this manufacture method, manufacturing process is simplified more, cost further reduces.
Perhaps, the manufacture method of laminated membrane laminated aluminium plate of the present invention is made up of following operation:
At least on a face of above-mentioned aluminium sheet, form the operation of first matrix resin layers,
On above-mentioned first matrix resin layers, form the resin bed that constitutes by second matrix resin that has with the above-mentioned first matrix resin intermiscibility operation and
More than the fusing point of above-mentioned first matrix resin and above-mentioned second matrix resin and the operation of heat-treating under the temperature below the decomposition point.
Adopt this manufacture method, be layered in by the matrix resin layers that will have intermiscibility on the face or two faces of aluminium sheet, implementing heat treatment more than the above-mentioned matrix resin layers fusing point and under the temperature below the decomposition point then, thereby make the interface of above-mentioned matrix resin interlayer form one, thereby can effectively promote the intermiscibility of above-mentioned matrix resin, and effectively carry out the formation one at above-mentioned interface.
In addition, among the present invention, when forming above-mentioned resin bed with intermiscibility, wherein, this intermiscibility is used to form two-layer or three-layer resin interface layer is pre-formed the resin bed that one forms, also can stackedly make the different mutually a plurality of resins of chemical constitution by mixing the resin that forms to certainty ratio, the temperature that stacked like this resin is heated to more than the fusing point makes the interface form one.For example, below when using two kinds of resins of A, B to be laminated into three layers as resin and with it with different mutually chemical constitutions, mix the method that two kinds of resins of this A, B make the interface form one and describe.
That is to say,, then, make and in advance two kinds of resins of A, B are pressed A/B=R in order to form the ground floor resin bed if the three-layer resin layer is decided to be ground floor, the second layer and the 3rd layer successively from the aluminium side
1=X
1/ Y
1The resin molding that mixes of ratio.Equally, the A of the resin molding that formation second layer resin bed is used, the mixed proportion of two kinds of resins of B are decided to be R
2=X
2/ Y
2, with form the A of the resin molding of three-layer resin layer usefulness, the mixed proportion of two kinds of resins of B is decided to be R
3=X
3/ Y
3At this moment, owing to all contain Resin A, B in ground floor～three-layer resin film,, can make the interface of these resin beds form one with comparalive ease so these interlaminar resins have intermiscibility.In addition, if the mixed proportion R of Resin A, B
1, R
2And R
3Numerical value be approaching as far as possible numerical value, the then easier interface that makes these resin beds forms one.
Description of drawings
Fig. 1 is the profile that schematically shows laminated membrane laminated aluminium plate structure of the present invention, and Fig. 1 (a) has three different resin beds, and the interface between these resin beds forms one; Fig. 1 (b) has two different resin beds, and the interface between these resin beds forms one.
Fig. 2 is the curve of the CONCENTRATION DISTRIBUTION of expression coloring pigment on the resin layer thickness direction of laminated membrane laminated aluminium plate M1.
Fig. 3 is the process chart that laminated membrane laminated aluminium plate M1 of the present invention is made in expression.
Fig. 4 is the profile that schematically shows laminated membrane laminated aluminium plate structure of the present invention, has the three-layer resin layer among the figure, and in these three layers, the superiors are identical with undermost resin bed, have only intermediate layer resin bed difference.
Fig. 5 is the curve of the CONCENTRATION DISTRIBUTION of expression coloring pigment on each resin layer thickness direction of laminated membrane laminated aluminium plate M2 of the present invention.
Fig. 6 is the schematic diagram of the necessary condition of the fusing point of contained each resin bed and decomposition point scope in the expression laminated membrane laminated aluminium plate of the present invention.
Fig. 7 is the profile that schematically shows a kind of in the past laminated resin material structure.
Fig. 8 is the figure that is used for illustrating the co-extrusion platen press principle that the manufacture method of laminated membrane laminated aluminium plate of the present invention adopts.
Fig. 9 is the schematic diagram of the interface state of the expression stacked film that is formed by Resin A, three kinds of different resin beds of resin B and resin C of the present invention.
The specific embodiment
Below describe embodiments of the present invention in detail.In addition, the present invention is not limited in these embodiments, so long as based on technological thought of the present invention, can suitably change.
Fig. 1 is the profile that schematically shows the structure of laminated membrane laminated aluminium plate of the present invention, Fig. 1 (a) has three layers of different resin bed on the aluminium sheet, this resin interface layer forms the figure of one, and Fig. 1 (b) has two-layer different resin bed, and this resin interface layer forms the figure of one.
With reference to Fig. 1 (a), laminated membrane laminated aluminium plate of the present invention is by forming first resin bed 1, second resin bed 2 and the 3rd resin bed 3 on given aluminium sheet A (below be called " aluminium sheet the A ") surface, and each interface completely is integral and constitutes.Perhaps with reference to Fig. 1 (b), be on the surface of given aluminium sheet A, to form first resin bed 1 and second resin bed 2, and each interface completely be integral constitute.Below the structure of the each several part that the present invention includes is described.
" aluminium sheet "
The aluminium sheet A that uses in the laminated membrane laminated aluminium plate of the present invention shown in Fig. 1 (a) and (b), can be according to the purposes of the final form of laminated membrane laminated aluminium plate, from known aluminium sheet of past or aluminium alloy plate, suitably select to use, when requiring shaping processability, the fine aluminium, 3000 that can use JIS 1000 to be is or 5000 aluminium alloys that are to be limited to this but have more than.
In addition, also can carry out this area known pre-treatment in the past, for example degreasing, carrying out washing treatment to this aluminium sheet A according to purpose corresponding to final form purposes, the processing of chromate, chromium phosphate hydrochlorate, trbasic zinc phosphate etc. etc., these pre-treatments can carry out separately or appropriate combination is carried out.By carrying out this pre-treatment, can improve the adaptation between resin bed 1 and aluminium sheet A, can improve the corrosion resistance of aluminium sheet A in addition.
Then, as described below, one or both sides at this aluminium sheet A, every layer applies or stacked given resin (first method), thereby perhaps be squeezed into belt course simultaneously and be stacked in upward stacked resin (second method) of aluminium sheet A by two or three resin that intermiscibility and fusion will be arranged mutually, implement given heat treatment then, can obtain laminated membrane laminated aluminium plate of the present invention.
" resin "
In the laminated membrane laminated aluminium plate of the present invention, can be at the stacked two-layer or three-layer resin layer of the one or both sides of above-mentioned aluminium sheet, the interface between these each resin beds of resin bed chien shih forms one integrated mass.Shown in Fig. 1 (a); the function that each resin bed required when resin bed formed three layers is: the function of the adaptation of maintenance of first resin bed and blank (aluminium sheet A); second resin bed waits in the processing that is shaped and adds that do not crack man-hour and variable color is suppressed to fully low function, and the 3rd resin bed waits the function that adds man-hour or protect second resin bed, first resin bed and blank when using in the processing that is shaped.Shown in Fig. 1 (b), resin bed forms that the function of each resin bed requirement is when two-layer: the function that first and second resin beds when first resin bed and second resin bed are all contrasted above-mentioned resin bed and be three layers have.
Therefore, must be not by means of continuous stacked this two-layer or three-layer resin layer of other layers.Otherwise, as long as continuous stacked this two-layer or three-layer resin layer formation one integrated mass as described below, and do not damage effect of the present invention, effect, also can there be other layers, for example between resin bed and aluminium sheet, there is adhesive layer, perhaps also can top coat be set again in the superiors of resin bed.
In laminated membrane laminated aluminium plate of the present invention, the matrix resin that constitutes each resin bed must have following character: between surperficial resin bed that forms of aluminium sheet A and aluminium sheet A required adaptation is arranged, and can give aluminium sheet A insulating properties.And above-mentioned resin must have following character: after being layered on the one or both sides of aluminium sheet A, soften by heating in temperature more than fusing point and the temperature range below the decomposition point, mix between different resin beds, the resin bed interface forms one.The resin that uses among the present invention is not particularly limited so long as satisfy the resin of above-mentioned condition and get final product.
As the resin that satisfies these necessary conditions of the present invention, generally can enumerate thermoplastic resin, specifically, for example acrylic acid series, ethene system, polyamide-based, fluorine system and polyester based resin.Wherein, polyamide-based resin and derivatives thereof such as the included nylon 66 of particularly polyamide-based resin, nylon 6, NYLON610, nylon 10, nylon 11, polyolefin-based resins such as polyethylene, polypropylene and derivative thereof, polyester based resin such as PET, polybutylene terephthalate, PEN and derivative thereof etc.In addition, constitute each resin bed of the present invention, the matrix resin that can constitute separately with these resins also can be with mixing the matrix resin that two kinds of resins form at least.
" combination of resin "
Set out by this viewpoint, particularly importantly, can determine to make it to satisfy the condition of each resin bed during the resin combination determining to use among the present invention different resins being built up layer by layer two-layer or three layers of temperature range that the stacked resin that forms is heat-treated.That is to say that as shown in Figure 6, above-mentioned stacked resin is by resin α (fusing point T
1℃, decomposition point T
4℃), resin β (fusing point T
2℃, decomposition point T
5℃) and resin γ (fusing point T
3℃, decomposition point T
6℃) under the occasion that constitutes, each the temperature range T below the above decomposition point of the fusing point of these resins
α, T
β, T
γBe respectively T
1≤ T
α≤ T
2, T
3≤ T
β≤ T
4, T
5≤ T
γ≤ T
6, these temperature ranges repeat mutually, for all these resin beds, must select to satisfy more than the fusing point and the temperature T of the following temperature of decomposition point
0The resin combination that exists.
In addition, the term that uses among the present invention " decomposition point " is meant, when forming laminated membrane laminated aluminium plate of the present invention, the matrix resin that constitutes the stacked film resin bed can keep the upper limit with the temperature range of the corresponding required rerum natura of its purpose.This decomposition point can suitably be selected according to the purpose purposes of laminated membrane laminated aluminium plate of the present invention, for example will use as target to the mass change of certainty ratio (for example 10% in), rerum natura variation etc.Generally with fusing point+100 ℃ as decomposition point, but be not particularly limited in this numerical value.
In addition, in order in above-mentioned heating-up temperature scope, to make the different resins interlayer have intermiscibility, wish that the macromolecular structure of above-mentioned different resins layer is similar mutually.
In other words, in laminated membrane laminated aluminium plate of the present invention, with each layer resin bed stacked be two layers or three layers of formation, but wish that these layers are made of mutual different matrix resin.That is to say, this be because, if resin bed is by forming with a kind of matrix resin, then the effect that obtains by stacked resin does not have clear and definite especially meaning, and by stacked different resin beds mutually, can make various requirement functions such as performance adaptation, aesthetic appearance or insulating properties etc., comprise the laminated membrane laminated aluminium plate of the present invention that resin bed with various different structures or composition forms and be achieved.
Therefore, generally select with the matrix resin of a series of thermoplastic resins as each layer.For example, can in each resin bed, use molecular structure (substituting group), molecular weight etc. to have polyamide-based resin, polyester based resin or the acrylic resin of some differences.As the representative polyamide-based resin that can use in the present invention, can enumerate for example nylon 66, nylon 6, NYLON610, nylon 10, nylon 11 etc.
Yet other serial resin that melting point resin and decomposition point as mentioned above is overlapping uses as the matrix resin of each resin bed, also within the scope of the invention.
In addition, be applicable to the resin bed (for example resin bed 1 among Fig. 1 (a) and the resin bed 10 among Fig. 1 (b)) on aluminium sheet A surface, preferably has desired adaptation with aluminium sheet A, in addition, for the resin bed that exposes on the surface (for example resin bed 3 among Fig. 1 (a) and the resin bed 20 among Fig. 1 (b)), preferably have rerum naturas such as mar proof or scratch-resistant.And, also can give hear resistance or hydrophobic oleophobic etc. according to the purposes of final form.
In addition, among the present invention, when being layered in resin bed on the aluminium sheet A and being 3 layers, these resin beds, can be made of whole different resin beds, can be same resin bed by the superiors and undermost resin bed also perhaps, and the resin bed that has only the intermediate layer is that different resin beds constitutes.
Wherein above-mentioned what is called " different resin beds " is meant the resin bed of formation as described below:
(1) macromolecular structure is mutually different.
(2) even macromolecular structure is identical, but the addition of the kind of additives such as additives such as molecular weight, coloring pigment, coloring pigment or coloring pigment etc. is different.
(3) have that a plurality of resins of identical macromolecular structure mix in varing proportions.
(4) will have the mixed with resin of same structure, and also be mixed with other resin in the matrix resin that in certain layer, uses.
In addition, among the present invention, when being layered in resin bed on the aluminium sheet A and being 3 layers, these resin beds, can be made of whole different resin beds, can be same resin bed by the superiors and undermost resin bed also perhaps, and the resin bed that has only the intermediate layer is that different resin beds constitutes.
These each layer matrix resins, can suitably select according to the purpose of each layer, for example, the matrix resin that constitutes the resin bed that directly contacts with aluminium sheet preferably has adherence with aluminium sheet, in addition, the preferred corrosion resistance of matrix resin, the resistance to chemical reagents of the formation the superiors are good.
The thickness of the resin bed when resin bed of the present invention is three layers, the thickness that preferably is in first resin bed of base material side is 0.5～20 micron, the thickness of second resin bed that forms on this first resin bed is 5～150 microns, and the thickness of the 3rd resin bed that forms on this second resin bed is 0.5～150 micron.Its reason is, if the thickness of first resin bed is less than 0.5 micron, then owing to substrate surface is difficult to be covered fully by this resin bed, so the adaptation between the base material and first resin bed becomes insufficient, first resin bed is peeled off from base material easily, if surpass 20 microns, then owing to the saturated economy that makes of adaptation with base material reduces, thereby not preferred.In addition, the thickness of second resin bed is in case less than 5 microns, then or be easy to generate irregular colour, perhaps be shaped to process to wait and add generation variable color easily in man-hour in enforcement, if surpass 120 microns, when then this resin bed solidified, it is superfluous that internal stress becomes, cause this resin bed to occur crackle easily or peel off, perhaps occur the improper situation that processing adaptation (having implemented to be shaped processing waits the adaptation after the processing) reduces easily.In addition, if the thickness of the 3rd resin bed is less than 0.5 micron, then is difficult to prevent fully the pin hole that produces inevitably in the resin bed; the misgivings that can not give full play to defencive function are arranged; if surpass 50 microns, then damage economy because of defencive function is saturated, thereby undesirable.In addition, the thickness of the resin bed when resin bed of the present invention is two layers, the thickness of first resin bed when being three layers with reference to above-mentioned resin bed respectively and the thickness of second resin bed.
" laminating method of resin bed "
As the method for the resin bed that forms laminated membrane laminated aluminium plate of the present invention, can adopt over the painting method of known various metallic plates or the method by stacked formation resin bed.When adopting painting method to form resin bed among the present invention, can be with coated with resins on aluminium sheet A such as roller coat device, make it dry form film after, filming to go up in this again forms other and films equally, thereby forms the stepped construction of two layers or three layers.At this moment, also can omit above-mentioned drying process in case of necessity.
In addition, the occasion of pasting the stacked resin of above-mentioned resin molding at aluminium sheet A last layer one deck, there is no particular restriction can be arranged on adhesive layer on the resin bed interface, as long as because the heat treatment that carry out when forming one at the resin bed interface hinders the characteristic of resin bed.In addition, also above-mentioned adhesive layer can be set, utilize pressure sintering etc. to make driving fit between resin bed, resin bed is laminated into two layers or three layers.
In addition, for laminated membrane laminated aluminium plate of the present invention, also can be on aluminium sheet patch laminate film and it is covered, described stacked film is to adopt a plurality of (two or three) that intermiscibility will be arranged mutually on one side one side different resins is squeezed into simultaneously and membranaceously carries out stacked co-extrusion platen press film forming and form.This co-extrusion pressure ratio juris as shown in Figure 8.As shown in Figure 8, the co-extrusion pressure rule that adopts in the manufacture method of laminated membrane laminated aluminium plate of the present invention is as being undertaken by following manner: use co-extrusion pressure device 40, the resin that this co-extrusion pressure device 40 has fusion is squeezed into membranaceous resin extruded portion 41 respectively and will be squeezed into the stacked roller 42 of membranaceous laminated resin by this resin extruded portion 41, Resin A and resin B are squeezed into sheet by resin extruded portion 41, this membranaceous Resin A and B that is squeezed into sheet is imported stacked roller 42, form the laminated resin film.There is no particular restriction for above-mentioned method with the stacked in advance formation laminated resin of a plurality of resins film, for example can adopt above-mentioned the sort of successively stacked method, or respectively with a plurality of resin mass heating and meltings, form a plurality of each resin molding with given thickness, simultaneously that these a plurality of resin moldings are bonding method by extruding.
" heat treatment "
After stacked resin-shaped becomes stacked resin bed on the one or both sides of aluminium sheet A, this stacked resin bed is implemented heat treatment like this, make the resin bed interface form one.This moment, the heating-up temperature of stacked resin bed was the temperature that above-mentioned resin bed fusing point is above and decomposition point is following.Above-mentioned resin bed is by the nylon 66 and the nylon 6 two-layer occasions that constitute of polyamide-based resin, their fusing point is respectively 260 ℃ and 215 ℃, definition according to above-mentioned decomposition point, the decomposition point of these resins is respectively 360 ℃ and 320 ℃ here, then can the heating-up temperature when the resin bed of stacked these resins is implemented heat treatment suitably determine in 260～320 ℃ scope.
In addition, can suitably adjust according to the kind or the heating-up temperature of resin heat time heating time.In the heating-up temperature scope of being determined by the fusing point of each resin and decomposition point, heating-up temperature is high more, the fused progress of resin just fast more.If heat time heating time is abundant, then resin reaches the state that abundant homogeneous distributes.(state of Fig. 9 " Z ")
To stacked resin bed on the one or both sides of aluminium sheet A like this,, can make above-mentioned resin interface layer two-layer or three layers stepped construction integrated by implementing heat treated more than the fusing point of each resin bed and under the temperature below the decomposition point.
In addition, when above-mentioned resin bed is made of 6 three layers of PET resin, above-mentioned nylon 66 and nylon, the fusing point of PET resin is 255 ℃, the fusing point of above-mentioned nylon 66 and nylon 6 is respectively 260 ℃ and 225 ℃, and the necessary heating-up temperature condition the when resin bed of stacked above-mentioned resin is implemented heat treatment is as described below.That is to say,, the decomposition point of PET resin is designated as T according to the definition of above-mentioned decomposition point
P℃, the decomposition point of above-mentioned nylon 66 and nylon 6 remembered respectively make T
N66℃ and T
N6 ℃, then because the decomposition point of common above-mentioned resin is higher than fusing point, thereby 255 ℃≤T
P, 260 ℃≤T
N66, 225 ℃≤T
N6,, require T for the interface that forms above-mentioned each resin bed forms the resin bed of one integrated mass
N6Be at least 260 ℃.T
N6Be lower than 260 ℃ occasion, the preferred heating-up temperature that the resin bed that makes above-mentioned each resin bed interface form one integrated mass forms usefulness does not exist.In this case, can adopt as described below by the resin that different resin beds is mixed to certainty ratio (below be called " hybrid resin "), thereby form the resin bed that the interface that makes above-mentioned each resin bed forms one integrated mass.Here said " interface of resin bed forms one integrated mass " is meant the state that the macromolecular chain of each resin bed twines mutually.The inventor etc. can confirm the mutual state that twines of macromolecular chain of this each resin bed by observe the section of the stacked film that contains in the laminated membrane laminated aluminium plate of the present invention with the light microscope interface.
" mixing of resin "
In the laminated membrane laminated aluminium plate of the present invention, modulate in advance the different resins hybrid resin to be mixed and made into as required to certainty ratio in order to form the resin bed that one integrated mass forms, to use.In addition, there is no particular restriction for the method for mixing different resins, suitably the known method of adopting over.For example nylon 6 and nylon 66 are mixed and made into the occasion of hybrid resin, in given container, drop into the nylon 6 and the nylon 66 of aequum respectively, on one side it is being heated more than fusing point of nylon 6 and nylon 66 and under the temperature below the above-mentioned decomposition point, carry out mechanical agitation on one side, thereby can make the hybrid resin of homogeneous.In addition, the hybrid resin to such preparation can add coloring pigment described later.
" coloring pigment "
In case of necessity, can in the layer laminate of laminated membrane laminated aluminium plate of the present invention, add coloring pigment.There is no particular restriction for the kind of these coloring pigments or characteristic, only otherwise influence the contained resin bed of the present invention interface formation one, can use.As this coloring pigment,, can use with titanium dioxide (TiO for example as the white color system coloring pigment
2) be the coloring pigment of base-material.
(occasion of three-layer resin layer makes the coloring pigment concentration maximum of intermediate layer resin bed)
When laminated membrane laminated aluminium plate of the present invention has the three-layer resin layer, from simplifying manufacturing process and the uniform viewpoint of CONCENTRATION DISTRIBUTION that makes coloring pigment, preferably only add coloring pigment in the intermediate layer in the three-layer resin layer, utilization makes the resin interface layer form one and the heat treatment carried out, makes upper strata or the lower floor of coloring pigment thermal diffusion to the intermediate layer.If constitute like this, can make the intermediate layer of CONCENTRATION DISTRIBUTION in the three-layer resin layer of coloring pigment produce Cmax.
(average grain diameter of coloring pigment)
In addition, the particle diameter of coloring pigment only otherwise be higher than the lower limit of above-mentioned each resin layer thickness that is to say, so long as get final product less than 0.5 micron, is not particularly limited.Disperse with given continuous CONCENTRATION DISTRIBUTION for this coloring pigment is passed between each resin bed, particle diameter is the smaller the better, but mainly practically from the economy aspect considers that the particle diameter of coloring pigment is 0.1～0.3 micron, average grain diameter be 0.2 micron suitable.
In addition, same with coloring pigment, also can make other additives (particle) pass each interlayer and disperse with given continuous CONCENTRATION DISTRIBUTION.
" first kind of embodiment "
(resin bed 1, resin bed 2 and resin bed 3 are mutually different stacked film)
First kind of embodiment that laminated membrane laminated aluminium plate of the present invention is made of mutual different resin bed 1, resin bed 2 and resin beds 3 below is described.The generalized section of the laminated membrane laminated aluminium plate M1 of first kind of embodiment of the present invention that reference is shown in Figure 1, the resin bed 3 three-layer resin layer L1 that the resin bed 1 that laminated membrane laminated aluminium plate M1 is formed by the last nylon 66 of aluminium sheet A, resin bed 2 and the nylon 66 identical with resin bed 1 macromolecular structure but that molecular weight is different that nylon 6 forms form constitute.In addition, the interface of resin bed L1 forms one, and allocating into titanium dioxide in this three-layer resin layer is that the coloring pigment of main component constitutes.
(CONCENTRATION DISTRIBUTION of coloring pigment)
In addition, Fig. 2 is that EPMA (electoron probe microanalysis: electron probe microanalysis) method, contained coloring pigment TiO in mensuration and the laminated membrane laminated aluminium plate M1 resin bed is used in expression
2Middle Ti atomic concentration has depth profiles (variation of the Ti signal strength signal intensity of the resin bed depth direction) result's of the Ti signal strength signal intensity of linear relationship curve map.Among Fig. 2, transverse axis is represented the degree of depth apart from resin bed L1 outmost surface, and the longitudinal axis is represented coloring pigment TiO among the resin bed L1
2The EPMA signal strength signal intensity of middle Ti atom.As shown in Figure 2, the depth profiles of Ti atom signals intensity has peak value among the resin bed L1 in resin bed 2, and is formed by resin bed 1 and resin bed 3 continuous distributed.
In addition, the resin bed L1 of laminated membrane laminated aluminium plate M1 is peeled off from aluminium sheet A, during with the interface state of observation by light microscope resin bed L1 section, can't see the border between resin bed at all.The result can prove thus, and the resin interface layer of laminated membrane laminated aluminium plate M1 of the present invention forms one.
(manufacture method)
The manufacture method of this laminated membrane laminated aluminium plate M1 of the present invention below is described.Fig. 3 is the process chart that laminated membrane laminated aluminium plate M1 of the present invention is made in expression.As shown in Figure 3, in order to improve the adaptation with resin bed, at first to do aluminium sheet A meet 1000 of JIS specification be fine aluminium and 3000 be alloy or 5000 be the good aluminium sheet of shaping processability such as alloy carry out surface of aluminum plate handle in degreasing, carrying out washing treatment commonly used, and then in order to improve the corrosion resistance of aluminium sheet A, in addition in order to improve the adaptation with resin bed, implement that surface of aluminum plate is commonly used in handling to change into processing.
Then, the coating that contains given resin with coating on aluminium sheet A such as known coater coating of past, brushing coating carries out stacked, perhaps the given resin molding that will make with the co-extrusion pressure method in advance be bonded in carry out on the aluminium sheet A stacked, perhaps will mix with predetermined ratio after a plurality of resin heats of solution, with mixed polymer be injected at continuously aluminium sheet A surface filming shape carry out stacked, thereby with resin bed stacked be three layers.Perhaps stacked every layer of resin bed becomes three layers on any substrate, then preformed resin film layer is stacked on the aluminium sheet A.
At this moment, if only in the resin bed of intermediate layer, add coloring pigment in the three-layer resin layer, then can omit the operation of adding coloring pigment to other resin beds, in the incorporate operation of resin interface layer of carrying out afterwards simultaneously, coloring pigment is upwards layer and lower floor's thermal diffusion from the intermediate layer, coloring pigment has continuous CONCENTRATION DISTRIBUTION as shown in Figure 2 in three resin beds.In addition, above-mentioned each heat more than the resin bed fusing point and in the temperature range below the decomposition point, the aluminium sheet A with stacked like this resin bed is implemented heat treatment.Like this, can obtain laminated membrane laminated aluminium plate M1 of the present invention.
" second kind of embodiment "
(the identical but resin bed of resin bed 1 and resin bed 32 different stacked film)
Followingly second embodiment of the present invention is described with reference to Fig. 4, the laminated membrane laminated aluminium plate of the present invention in this embodiment, identical by resin bed 100 with resin bed 300, and have only resin bed 200 different resin beds to constitute.Wherein identical with above-mentioned first embodiment structure is only put down in writing the result and is omitted explanation to it.As shown in Figure 4, laminated membrane laminated aluminium plate M3, the resin bed of forming by the nylon on the aluminium sheet A 66 100, the resin bed 200 that nylon 6 is formed and with resin bed 100 have identical macromolecular structure only the resin bed formed of the different nylon 66 of molecular weight form for 300 3 layers.And the interface of resin bed L3 formation one, having allocated into titanium dioxide in this three-layer resin layer is the coloring pigment of main component.
(CONCENTRATION DISTRIBUTION of coloring pigment)
In addition, same with first embodiment, with the depth profiles of contained coloring pigment concentration in the resin bed of EPMA method mensuration laminated membrane laminated aluminium plate M3, obtained and the identical result of accompanying drawing 2 cardinal principles.That is to say and find out that the CONCENTRATION DISTRIBUTION of this titanium atom has the peak in resin bed 20 districts, and in resin bed 100 and resin bed 300 continuous distributed.
The resin bed L3 of laminated membrane laminated aluminium plate M3 is peeled off from aluminium sheet A,, do not see the border between resin bed at all with the section of metallurgical microscopes visualization resin bed L3.Prove that by these results the interface between laminated membrane laminated aluminium plate M3 resin bed of the present invention forms one.
(manufacture method)
The manufacture method of this laminated membrane laminated aluminium plate M2 of the present invention below is described.Wherein, for the operation of using in can mutatis mutandis above-mentioned first kind of embodiment, the operation of making laminated membrane laminated aluminium plate M2 of the present invention is illustrated with Fig. 3.As shown in Figure 3, in order to improve the adaptation with resin bed, be fine aluminium at first to 1000 of the JIS specification that meets of making aluminium sheet A, and meet 3000 of JIS specification is or shaping processability such as 5000 line aluminium alloys is good aluminium sheet and implement degreasing, the carrying out washing treatment that surface of aluminum plate adopts in handling usually, and then in order to improve the corrosion resistance of aluminium sheet A, in addition in order to improve the adaptation with resin bed, implement the processing that changes into that surface of aluminum plate adopts in handling usually.
Then, coating contains the coating of given resin on aluminium sheet A, perhaps with the film-stack of given resin on aluminium sheet A, thereby resin bed is laminated into three layers.Perhaps after whenever folded layer by layer resin bed becomes three layers on any substrate, preformed resin film layer is stacked on the aluminium sheet A.Then, above-mentioned each heat more than the resin bed fusing point and in the temperature range below the decomposition point, the aluminium sheet A that has stacked resin bed is like this implemented heat treatment.Like this, can obtain laminated membrane laminated aluminium plate M3 of the present invention.
" the third embodiment "
(stacked film) with resin bed 1 and resin bed 2
Following with reference to Fig. 1 (b), the third embodiment that is made of different two kinds of resin beds 10 and resin bed 20 two-layer laminate is described in the laminated membrane laminated aluminium plate of the present invention.
Wherein, for only putting down in writing the result, omit its explanation with the same structure of above-mentioned first, second kind embodiment.Shown in Fig. 1 (b), the resin bed 20 two layers of resin layer L3 that resin bed 10 that laminated membrane laminated aluminium plate M2 is formed by nylon 66 on aluminium sheet A and nylon 6 form constitute.In addition, the interface of resin bed L2 forms one, and allocating into titanium dioxide in this resin bed L2 is that the coloring pigment of main component constitutes.
(CONCENTRATION DISTRIBUTION of coloring pigment)
In addition, Fig. 5 and above-mentioned first kind of embodiment and second kind of embodiment are same, are that the XPS method is used in expression, measure and the contained coloring pigment TiO of laminated membrane laminated aluminium plate M2 resin bed
2The curve map that middle Ti atomic concentration has depth profiles (variation of the Ti signal strength signal intensity of the resin bed depth direction) result of the EPMA signal strength signal intensity of linear corresponding relation.Among Fig. 5, transverse axis is represented the thickness apart from the depth direction of resin bed L2 outmost surface, and the longitudinal axis is illustrated in the concentration of Ti atom contained in the coloring pigment of resin bed L2.As shown in Figure 4, the depth profiles of Ti atom has peak value in resin bed 2, and in resin bed 1 and resin bed 3 continuous distributed.
In addition, the resin bed L2 that goes up laminated membrane laminated aluminium plate M2 from aluminium sheet A peels off, and when using the section of metallurgical microscopes perusal resin bed L, can not see the border between resin bed L2 fully.These results prove that the resin interface layer of laminated membrane laminated aluminium plate M2 of the present invention forms one.
(manufacture method)
The manufacture method of this laminated membrane laminated aluminium plate M2 of the present invention below is described.Wherein, for the operation of using in can mutatis mutandis above-mentioned first kind of embodiment, the operation of making laminated membrane laminated aluminium plate M2 of the present invention is illustrated with Fig. 3.As shown in Figure 3, in the present embodiment, in order to improve the adaptation with resin bed, be fine aluminium at first to 1000 of the JIS specification that meets of making aluminium sheet A, and meet 3000 of JIS specification is or shaping processability such as 5000 line aluminium alloys is good aluminium sheet and implement degreasing, the carrying out washing treatment that surface of aluminum plate adopts in handling usually, and then,, implement the processing that changes into that surface of aluminum plate adopts in handling usually in addition in order to improve the adaptation with resin bed in order to improve the corrosion resistance of aluminium sheet A.
Then, coating contains the coating of given resin on aluminium sheet A, perhaps with the film-stack of given resin on aluminium sheet A, thereby resin bed is laminated into two layers or three layers.Perhaps become two layers or three layers and preformed resin molding by whenever folded layer by layer resin bed on any substrate stacked on the aluminium sheet A, perhaps with two or three resin mass difference heating and melting, extruding forms two or three resin molding with given thickness, simultaneously with the bonding and preformed resin molding of these resin moldings.At this moment, above-mentioned each heat more than the resin bed fusing point and in the temperature range below the decomposition point, the aluminium sheet A that has stacked resin bed is like this implemented heat treatment.Like this, can obtain laminated membrane laminated aluminium plate M2 of the present invention.
[embodiment]
Below, the various samples of the comparative example of the embodiment of the necessary condition of the present invention of explanation and discontented unabridged version invention necessary condition were estimated more than preparation was satisfied.Wherein the present invention is not limited in these embodiment, as long as just can suitably change based on technological thought of the present invention.Each formation for test agent contained stacked film of these embodiment and comparative example has been shown in the table 1, in addition, has illustrated in the table 2 and used these, the result of the evaluation test that processability and adaptation are carried out for test agents.In addition, these embodiment and comparative example all adopt above-mentioned technological process shown in Figure 3 for test agent, the stacked film shown in the table 1 is layered on the base material of JISAA 1100-H24 (0.30 millimeter of thickness of slab) and makes.
In addition, " mixed with resin state " in the so-called table 2 refers to that stacked resin heat-treats the interface state of the resin bed of formation (stacked film) result that (light microscope) observe that detects by an unaided eye as shown in Figure 9.That is to say that Fig. 9 represents the interface state of the stacked film that formed by Resin A, three kinds of different resin beds of resin B and resin C, the interface of state " X " expression Resin A, resin B and resin C (perhaps Resin A and resin B) is in clear and definite state; Almost completely merge at the interface of state " Y " expression Resin A, resin B and resin C, but Resin A, resin B and resin C are in the state that the comparison heterogeneity distributes; Almost completely merge at the interface of state " Z " expression Resin A, resin B and resin C, and Resin A, resin B and resin C are in the state that abundant homogeneous distributes.
Table 1
| No. | The formation of stacked film (with base material contact surface side resin bed/face side resin bed) |
| A1 | Nylon 6 (215 ℃ of fusing points, 10 microns of thickness)/nylon 66 (260 ℃ of fusing points, 10 microns of thickness) |
| A2 | Nylon 6 (215 ℃ of fusing points, 10 microns of thickness)/nylon 66 (260 ℃ of fusing points, 10 microns of thickness) |
| A3 | PET copolymer (220 ℃ of fusing points, 5 microns of thickness)/PET homopolymers (255 ℃ of fusing points, 15 microns of thickness) |
| A4 | PET copolymer (220 ℃ of fusing points, 5 microns of thickness)/PET copolymer (220 ℃ of fusing points, 10 microns of thickness, TiO 2: contain 20 quality %)/PET copolymer (220 ℃ of fusing points, 5 microns of thickness) |
| A5 | PET copolymer (220 ℃ of fusing points, 5 microns of thickness, TiO 2: contain 10 quality %)/PET copolymer (220 ℃ of fusing points, 10 microns of thickness, TiO 2: contain 50 quality %)/PET copolymer (220 ℃ of fusing points, 5 microns of thickness, TiO 2: contain 10 quality %) |
| A6 | PET copolymer (220 ℃ of fusing points, 5 microns of thickness, TiO 2: contain 35 quality %)/PET copolymer (220 ℃ of fusing points, 10 microns of thickness, TiO 2: 60 quality %)/PET copolymer (220 ℃ of fusing points, 5 microns of thickness, TiO 2: 35 quality %) |
Annotate 1): TiO
2Pigment
Table 2
| Classification | No. | The heat treatment temperature of stacked film and proterties | Evaluation result | |||
| The formation No. of stacked film 1) | The admixture of resin 2) | Heat treatment temperature (℃) | Processability 3) | Adaptation 4) | ||
| Embodiment | 1 | A1 | Y | 265 | ◎ | ○ |
| 2 | A1 | Z | 280 | ◎ | ◎ | |
| 3 | A2 | Y | 280 | ◎ | ◎ | |
| 4 | A3 | Y | 280 | ◎ | ◎ | |
| 5 | A4 | Y | 240 | ◎ | ◎ | |
| 6 | A5 | Z | 225 | ◎ | ○ | |
| 7 | A5 | Y | 240 | ◎ | ◎ | |
| 8 | A6 | Y | 240 | ◎ | ◎ | |
| Comparative example | 9 | A1 | X | 205 | △ | × |
| 10 | A1 | X | 225 | ○ | △ | |
| 11 | A3 | X | 215 | ○ | △ | |
| 12 | A5 | X | 215 | ○ | △ | |
Annotate 1): with reference to table 1,
Annotate 2): the interface of state " X " expression Resin A, resin B and resin C (perhaps Resin A and resin B) is in clear and definite state; Almost completely merge at the interface of state " Y " expression Resin A, resin B and resin C, but Resin A, resin B and resin C are in the state that the comparison heterogeneity distributes; Almost completely merge at the interface of state " Z " expression Resin A, resin B and resin C, and Resin A, resin B and resin C are in the state that abundant homogeneous distributes.(with reference to Fig. 9)
Annotate 3): " ◎ " (fabulous): resin molding can not be peeled off from aluminium sheet fully
" zero " (well): the stacked film below 1 millimeter is peeled off has only a place
" △ " (in practicality out of question but many shortcomings occur): the stacked film below 1 millimeter is peeled off 2～3 places
" * " (bad): can find to peel off more than 1 millimeter.
Annotate 4): " ◎ " (fabulous): peel strength more than 3N/20mm,
" zero " (well): peel strength below the above 3N/20mm of 2N/20mm,
" △ " (in practicality out of question but many shortcomings occur): peel strength below the above 2N/20mm of 1N/20mm,
" * " (bad): peel strength is below 1N/20mm.
As shown in table 1, the comparative example of embodiment that satisfies necessary condition of the present invention and discontented unabridged version invention necessary condition for test agent in stacked film A1～A6 of using all be by constituting between the more approaching polymer of intermiscibility and fusing point arranged mutually.
That is to say that each stacked film of A1 and A2 is made of the nylon 6 of 215 ℃ of fusing points, 10 microns of the bed thickness double-layer structure that combines with the nylon 66 of 260 ℃ of fusing points, 10 microns of bed thickness.In addition, the stacked film of A3 is made of the double-layer structure that PET (PET) copolymer of 220 ℃ of fusing points, 5 microns of bed thickness and 255 ℃ of fusing points, the PET homopolymers of 15 microns of bed thickness form.
In addition, A4, each stacked film of A5 and A6 is by 220 ℃ of fusing points, the PET copolymer that bed thickness is 5 microns, 220 ℃ of fusing points, 220 ℃ of PET copolymer that bed thickness is 10 microns and fusing points, the three-decker that the PET copolymer that bed thickness is 5 microns constitutes, wherein, A4 only contains 20 quality % titanium dioxide as pigment in the intermediate layer, A5 contains 10 quality % titanium dioxide in the contact surface side resin bed that contacts with base material, contain 50 quality % titanium dioxide in the intermediate layer, contain 10 quality % titanium dioxide in addition in the outmost surface side resin bed, and, A6 contains 35 quality % titanium dioxide in the contact surface side resin bed that contacts with base material, contain 60 quality % titanium dioxide in the intermediate layer, in outmost surface side resin bed, contain 35 quality % titanium dioxide in addition.
Therefore, utilize above-mentioned method shown in Figure 3, will have the stacked film of forming shown in the table 1 and be layered on the A1 plate of JISAA 1100-H24 (0.30 millimeter of thickness of slab), make the test agent that supplies shown in the table 2, estimate the processability and the adaptation of these samples.Evaluation as the stacked film processability, adopt following method: use to have each confession test agent of forming shown in the table 2, make 10 millimeters of diameters, 20 millimeters sizes of length and be the stretching attenuate calotte that stretching-attenuate of 20% processes through reduction, again this stretching attenuate calotte is repaired, estimated the state of trim part stacked film.The standard of this evaluation is: resin molding can not be chosen as " ◎ " (fabulous) from what aluminium sheet was peeled off fully; Stacked film below 1 millimeter peel off have only a place be chosen as " zero " (well); Stacked film below 1 millimeter is peeled off being chosen as of 2～3 places " △ " (in the practicality out of question but many shortcomings are arranged); That can find to peel off more than 1 millimeter is chosen as " * " (bad).
In addition, evaluation as the stacked film adaptation, measuring through rolling rate is that the above-mentioned JIS 5000 of 50% cold-rolling treatment is 180 ℃ of peel strengths between alloy (AA1100-H24) and the stacked film, peel strength being evaluated as more than 3N/20mm " ◎ " (fabulous); Peel strength is evaluated as " zero " (well) below the above 3N/20mm of 2N/20mm; Peel strength being evaluated as below the above 2N/20mm of 1N/20mm " △ " (in the practicality out of question but many shortcomings are arranged); Peel strength is evaluated as " * " (bad) below 1N/20mm.
Wherein, satisfying embodiment No.1～8 of necessary condition of the present invention and comparative example No.9～12 of discontented unabridged version invention necessary condition all is to adopt two or three resin mass difference heating and melting, simultaneously these resin extruded are become the membranaceous stacked co-extrusion platen press of carrying out, formation has the laminated resin film of given thickness, is attached to then on the above-mentioned aluminium sheet.
As shown in table 2, heat treatment has all been implemented more than the resinous fusing point and under the temperature below the above-mentioned decomposition point in heat treatment temperature in by above-mentioned each stacked film in embodiment No.1～8 of satisfying necessary condition of the present invention.On the other hand, heat treatment is being implemented below the heat treatment temperature fusing point resinous by above-mentioned each stacked film or under the temperature more than the above-mentioned decomposition point in comparative example No.9～12 of discontented unabridged version invention necessary condition.
As can be seen as shown in table 2, embodiment No.1～8 visualizations (light microscope) of satisfying necessary condition of the present invention to the mixed with resin state all be in state " Y " (almost completely merge at the interface, each resin is in the state that the comparison heterogeneity distributes) or state " Z " (almost completely merge at the interface, each resin is in the state that abundant homogeneous distributes), the interface becomes one, forms stacked film.In addition, the result of processability and adaptation evaluation also is " ◎ " (fabulous) or " zero " (well), in addition, through visual valuation do not find the to be shaped appearance of the irregular colour that processing causes, as can be seen, even the shaping processing that experience is harsh peeling off between resin bed also do not occur, and the adaptation between resin bed and the aluminium sheet also can keep abundant.
Relative therewith, in comparative example No.9～12 of discontented unabridged version invention necessary condition, think visualization (light microscope) to the mixed with resin state all be in state " X ", resin bed forms with the state that the interface clearly exists.The evaluation result of shaping processability and adaptation is " △ " (in practicality out of question but shortcoming is arranged at part place) or " * " (bad), through the visual valuation irregular colour that processing causes of can finding to be shaped, implement harsh shaping and add man-hour, occur between resin bed peeling off, the adaptation between resin bed and the aluminium sheet can not keep.
Above presentation of results even embodiments of the invention all can keep between resin bed and the adaptation between resin bed and aluminium sheet through harsh shaping processing, irregular colour do not occur simultaneously yet, is a kind of laminated membrane laminated aluminium plate that is suitable for using in the capacitor case.
Claims (8)
1, a kind of laminated membrane laminated aluminium plate, be on a face of aluminium sheet that is main component, to be laminated to the laminated membrane laminated aluminium plate that few two layers of resin layer forms at least with aluminium, wherein said resin bed is made of polyester based resin, it is characterized in that, the matrix resin that constitutes above-mentioned each resin bed is the resin with intermiscibility, in above-mentioned resin bed, sneak into coloring pigment in one deck at least, at the stacked above-mentioned resin bed of heat treatment more than the fusing point of the whole matrix resins that constitute above-mentioned each resin bed and under the temperature below the decomposition point.
2,, sneak into coloring pigment in the above-mentioned resin bed and pass between above-mentioned each resin bed and disperse with given continuous CONCENTRATION DISTRIBUTION according to the described laminated membrane laminated aluminium plate of claim 1.
3, according to the described laminated membrane laminated aluminium plate of claim 1, above-mentioned resin bed constitutes by three layers at least, and in above-mentioned three layers, the coloring pigment CONCENTRATION DISTRIBUTION in intermediate layer is the highest.
4, according to the described laminated membrane laminated aluminium plate of claim 1, it is characterized in that, each interface between above-mentioned resin bed, above-mentioned matrix resin spreads mutually to each resin bed becomes one integrated mass.
5,, sneak into coloring pigment in the above-mentioned resin bed and pass between above-mentioned each resin bed and disperse with given continuous CONCENTRATION DISTRIBUTION according to the described laminated membrane laminated aluminium plate of claim 4.
6, according to the described laminated membrane laminated aluminium plate of claim 4, above-mentioned resin bed constitutes by three layers at least, and in above-mentioned three layers, the coloring pigment CONCENTRATION DISTRIBUTION in intermediate layer is the highest.
7, the manufacture method of the described laminated membrane laminated aluminium plate of claim 1, form by following operation:
Adopt on one side incite somebody to action mutual by intermiscibility and by at least two kinds of matrix resins that different resins is formed be squeezed into simultaneously membranaceous carry out stacked film that stacked co-extrusion pressure method makes cover at least one face of above-mentioned aluminium sheet operation and
More than above-mentioned whole matrix resin fusing points and the operation of heat-treating under the temperature below the decomposition point,
Wherein said resin is made of polyester based resin.
8, the manufacture method of the described laminated membrane laminated aluminium plate of claim 1, form by following operation:
On at least one face of above-mentioned aluminium sheet, form the operation of first matrix resin layers;
On above-mentioned first matrix resin layers, form by having the operation of the resin bed that second matrix resin of intermiscibility forms with above-mentioned first matrix resin; With
More than the fusing point of above-mentioned first matrix resin and above-mentioned second matrix resin and the operation of heat-treating under the temperature below the decomposition point,
Wherein said resin bed is made of polyester based resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001101162A JP2002292784A (en) | 2001-03-30 | 2001-03-30 | Laminated film laminated aluminum panel and method for manufacturing the same |
| JP2001101162 | 2001-03-30 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1382582A CN1382582A (en) | 2002-12-04 |
| CN1254367C true CN1254367C (en) | 2006-05-03 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021087687A Expired - Fee Related CN1254367C (en) | 2001-03-30 | 2002-04-01 | Laminated membrane laminated aluminium plate and its mfg. method |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2002292784A (en) |
| KR (1) | KR100481612B1 (en) |
| CN (1) | CN1254367C (en) |
| MY (1) | MY136512A (en) |
| TW (1) | TWI224555B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100675777B1 (en) * | 2005-04-22 | 2007-02-02 | 엘지전자 주식회사 | Vertical hinge hinge device of refrigerator door |
| CN102473866B (en) * | 2009-08-07 | 2015-09-09 | 大日本印刷株式会社 | Packaging materials for electrochemical cells |
| JP5110132B2 (en) * | 2009-08-07 | 2012-12-26 | 大日本印刷株式会社 | Packaging materials for electrochemical cells |
| JP5556128B2 (en) | 2009-10-30 | 2014-07-23 | ソニー株式会社 | Non-aqueous electrolyte battery |
| KR200451908Y1 (en) * | 2010-07-16 | 2011-01-18 | 주식회사 공진 | Support frame for hinge of refrigerator |
| JP6259719B2 (en) * | 2014-06-06 | 2018-01-10 | 株式会社村田製作所 | Nonaqueous electrolyte battery and exterior material for nonaqueous electrolyte battery |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3958867B2 (en) * | 1998-06-02 | 2007-08-15 | 東洋鋼鈑株式会社 | Method for producing colored polyester film, method for producing colored polyester film-coated metal plate, and method for processing can |
-
2001
- 2001-03-30 JP JP2001101162A patent/JP2002292784A/en active Pending
-
2002
- 2002-03-27 MY MYPI20021101A patent/MY136512A/en unknown
- 2002-03-28 TW TW091106198A patent/TWI224555B/en not_active IP Right Cessation
- 2002-03-29 KR KR10-2002-0017462A patent/KR100481612B1/en not_active Expired - Fee Related
- 2002-04-01 CN CNB021087687A patent/CN1254367C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002292784A (en) | 2002-10-09 |
| CN1382582A (en) | 2002-12-04 |
| TWI224555B (en) | 2004-12-01 |
| KR100481612B1 (en) | 2005-04-08 |
| MY136512A (en) | 2008-10-31 |
| KR20020077264A (en) | 2002-10-11 |
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