CN102189720B - Composite board combining metal substrate and outer decoration layer and manufacturing method for composite board - Google Patents
Composite board combining metal substrate and outer decoration layer and manufacturing method for composite board Download PDFInfo
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- CN102189720B CN102189720B CN 201010118410 CN201010118410A CN102189720B CN 102189720 B CN102189720 B CN 102189720B CN 201010118410 CN201010118410 CN 201010118410 CN 201010118410 A CN201010118410 A CN 201010118410A CN 102189720 B CN102189720 B CN 102189720B
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Abstract
The invention discloses a composite board combining a metal substrate and an outer decoration layer and a manufacturing method for the composite board. The manufacturing method comprises the following steps of: hot-pressing a first thermoplastic rubber (TPR) adhesive layer with the thickness of about 400 to 500 micrometers on the surface of the metal substrate, wherein the first TPR adhesive layer is a thermoplastic rubber film formed by synthesizing butylbenzene segmented copolymer with hydrogen carbonide petroleum resin; penetrating the first TPR adhesive layer into a fine concave hole existing on the surface of the metal substrate until part of the thickness, such as 10 percent of the thickness (about 40 to 50 micrometers) of the first TPR adhesive layer is reduced; thermally pasting asecond TPR adhesive layer with the thickness of about 400 to 500 micrometers on the surface of the outer decoration layer in a roller mode to ensure that the second TPR adhesive layer is not penetrated into a fine hole existing on the surface of the outer decoration layer; and performing a primary hot-pressing adhesion process to ensure that the metal substrate and the outer decoration layer are mutually hot-pressed through the first TPR adhesive layer and the second TPR adhesive layer to form the stable adhesively-combined integrated composite board. The composite board can be used for deep processing molding operation to prepare a shell-shaped object with the advantages of high intensity and aesthetic decorative appearance, and the defects of poor adhesive effects, low molding quality and relatively limited outer decoration layer materials in the prior art are overcome.
Description
Technical field
The present invention relates to composite board and the manufacture method thereof of a kind of metal substrate and outer finishing coat, espespecially a kind of surface at metal substrate and outer finishing coat fit respectively first one the one TPR adhesion layer and one the 2nd TPR adhesion layer, this TPR is the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols, again by hot pressing bonding process make this outer finishing coat and metal substrate via first and second set on surface TPR adhesion layer mutually hot pressing fit to form the integral type composite board, for being applied to make housing shape thing.
Background technology
Various electronic products on the market, including but not limited to common computer (computer) product such as mobile computer (Notebook computer, be called for short NB), communication (communication) product such as the 3C Products such as mobile phone or consumer (consumer) product, housing commonly used is as the shell of product; This housing has different structures with the designing requirement of product, and if with regard to the employed material of matrix (base) of housing, can roughly be divided into two primary structure classifications of polymer housing and metal shell.
Polymer housing with external decorative cover generally is to utilize to embed die type trailing (in-molddecorating process, be called for short IMD) make, it is with formation three-dimensional space forming shape and prints figuratum carrier (substrate) such as the polymer film, hereinafter to be referred as IMD film (IMD film), be embedded in the mould, recycling plastic ejection moulding technique make the thermoplastic resin ejection formation at the back side of this IMD film to form the matrix of this housing, hereinafter to be referred as resin matrix (resin base), this resin matrix is combined with the IMD film is integrally formed formula polymer housing, wherein, this IMD film (IMD film) can the secure bond mode be located on the outer surface of resin matrix (resin base) and forms a permanent device thing, is provided as an outer decorative cover of this polymer housing or a protective surface or the two all is; In addition, this IMD film temporarily fixed form is located on the outer surface of resin matrix (resin base) and forms a temporary rig, this IMD film can be torn off after finishing, and make the printed patterns transfer printing on this IMD film or be deposited in an outer decorative cover that is provided as this polymer housing on the outer surface of resin matrix.
There are a lot of prior aries at present in structural design and manufacture method thereof for above-mentioned polymer housing, comprise:
US3,654,062 has disclosed have the laminated type surface patch correlation technique of molded plaque (a molded decorative plaque) of (a laminated facing sheet), and it is that the hot melting plastic ejection formation has been had on the back side of pressing surface patch of mold structure and forms one.US6,117,384 have disclosed the film that utilization has colorful color, the thermoplastic resin ejection formation are consisted of the method correlation technique of the solid object of permanent combination at the back side of this film again.US4,391,954 have disclosed the correlation technique that comprises aromatic carbonate salt polymer (aromaticcarbonate polymer) and the molded complex of thermoplastics type (thermoplastic molding composition) of the polynary ester (polyester) of being obtained by cyclohexane family (cyclohexanedimethanol).US4,125,572 have disclosed the correlation technique that comprises aromatic carbonate salt polymer (aromatic carbonate polymer) and the molded complex of thermoplastics type (thermoplastic molding composition) of the polynary ester (polyester) of being obtained by aliphatic (aliphatic) or cycloaliphatic (cycloaliphatic diol).US6,465,102 have disclosed and have comprised article and a method of moulding thereof of decorating the polymer matrix (polymeric base) that forms with surf zone and integral type, and this polymer matrix comprises the polynary ester resin of transparent cycloaliphatic (cycloaliphatic polyester resin), wherein the polynary ester resin of this cycloaliphatic is the correlation technique (An article comprising a decorativesurface area and an integral formed polymeric base comprising transparentcycloaliphatic polyester resin, wherein the cycloaliphatic polyester resin is free froman aromatic moiety and the method for molding thereof) that not disturbed by aromatic series part (aromatic moiety).US6,117, the 384 embedding die types that disclosed improvement are decorated the correlation technique with technique (in-mold decorating process, IMD).US6,136,441 have disclosed the correlation technique of multiple field polymer article (multilayer plastic articles).The patent specification content of the prior aries such as the structural design of the above-mentioned various relevant polymer housings of reference or manufacture method, these prior aries mostly are that polymer film (being the IMD film) and resin matrix (resin base) that a polymer housing comprises are made respectively further restriction (limitation) as can be known, as polymer film (IMD film) or resin matrix (resin base) being defined as a certain special chemical family plastic material, thereby make a firm integral type composite plastic lumber in conjunction with being difficult for peeling off, and again can and other patent (prior art) between having any different property.
Yet, when the polymer film (being the IMD film) of the polymer housing article that are made of composite wood and/or resin matrix (resin base) are becomed privileged respectively when limiting, employed material is restricted, the application of polymer film (being the IMD film) and/or resin matrix (resin base) is restricted relatively, be unfavorable for the application of made polymer housing, for example need to want to select including but not limited to cloth cover for variation, leathering, when the materials such as resin fibre face are used as the polymer film, then often can't utilize identical technology or equipment and reach the production efficiency height, but mass production and the good effect of quality keyholed back plate, relatively can't promote service efficiency and the range of application of this polymer shell, therefore can be considered the shortcoming of above-mentioned these polymer housing article.
In addition; more common metal shell comprises: the hull shape thing of making by machining with sheet metal such as aluminium alloy sheet; or further on the outer surface of this metal shell shape thing, do in addition surface processing and process to present gloss or pattern; or a resin bed such as resin film further are set in addition again in order to protect outer metallic surface to be scraped with in avoiding using on the outer surface of this metal shell shape thing; bump equivalent damage; or the figuratum resin bed of one deck tool is set in addition on the outer surface of this metal shell shape thing further; in order to aesthetic appearance or the sense of touch of protecting outer metallic surface and promoting product; or with the assembling of interiors of products assembly need utilize plastic ejection moulding technology or the bonding set mode of injection moulding (only referring to the molding mode by injection mo(u)lding) directly on the inner surface of this metal shell shape thing the place, right position arrange or the various assemblings of bonding set polymer member such as flange shape thing or floor shape thing; use structure and the integral thickness of polymer member in order to simplify these assemblings, and promote structural strength.
Structural design and manufacture method thereof for above-mentioned metal shell, there have been at present a lot of prior aries, comprise U.S. patent of invention US5,695,699, US5,472,782 and U.S.'s patent of invention openly invent US2009/0117401, US2008/0127479, US2007/0218721 etc., existing illustrate respectively with following patent:
Chinese invention patent application ZL02805359.1 (International Application Serial No. PCT/JP2002/007267, international publication WO2003/064150) complex of a kind of aluminium alloy and resin and the correlation technique of manufacture method thereof have been disclosed, it is characterized in that, comprise: through the aluminium alloy shape thing of contact operation, described contact operation is to make aluminium alloy shape thing and dissolving be selected from ammonia, hydrazine (diamine), the aqueous solution contact of the compound of more than one in methyl amine and the ethylenediamine, make above-mentioned adsorption from aqueous solution, remain in its surperficial operation, with the resin that is attached to integratedly aforementioned aluminium alloy shape thing by injection mo(u)lding, described resin is selected from polyalkylene terephthalates, copolymer take aforementioned polyalkylene terephthalates as main body, with in the thermoplastic compounds that contains aforementioned polyalkylene terephthalates composition more than one.
Chinese invention patent application ZL200380102886.0 (International Application Serial No. PCT/JP2003/014213, international publication WO2004/041532) complex of a kind of aluminium alloy and resin and the correlation technique of manufacture method thereof have been disclosed, it is characterized in that, by through the aluminium alloy shape thing of the dipping process that in being selected from more than one the aqueous solution of ammonia, hydrazine (diamine) and water-soluble amine compound, floods and be attached to integratedly on the surface of described aluminium alloy shape thing, contain the thermoplastic compounds formation of polyphenylene sulfide composition.
Chinese invention patent application ZL200380104500.X (International Application Serial No. PCT/JP2003/014214, international publication WO2004/041533) complex of a kind of aluminium alloy and resin and the correlation technique of manufacture method thereof have been disclosed, it is characterized in that, be that 5 μ m～50 μ m and its surface have fine recess below the 1 μ m or the aluminium alloy shape thing of protuberance by surface roughness, fix with immersing described recess or protuberance, average coefficient of linear expansion is 2～4 * 10 in length and breadth
-5℃
-1The thermoplastic compounds take polybutylene terephthalate (PBT) resin or polyphenylene sulfide as main component consist of.
Chinese invention patent application ZL200680046075.7 (International Application Serial No. PCT/JP2006/324493, international publication WO2007/066742) disclosed the correlation technique of a kind of metal-resin composite and manufacture method thereof, it is characterized in that, formed by aluminium alloy element and thermoplastic synthetic resin composition member, described aluminium alloy element is such as lower member: be selected from ammonia through impregnated in, the operation of the aqueous solution of more than one of callosity (diamine) and water-soluble amine compound, use electron microscope observation, its surface is the recess covering of 10～80nm by the number average internal diameter, described thermoplastic synthetic resin composition member is such as lower member: through injection mo(u)lding and as described in being bonded to aluminium alloy element as described on the surface, and the main component of resinous principle in forming is polyamide, submember is the resistance to impact improved materials.
Yet, above-mentioned Chinese invention patent ZL02805359.1, ZL200380102886.0, ZL200380104500.X and ZL200680046075.7 disclose metal and the complex of resin and the correlation technique of manufacture method thereof, and its individual features all is, this metal (such as aluminium alloy) shape thing is the dipping process of dipping in the aqueous solution (such as more than one the aqueous solution of water-soluble amine compound) through special selection, and again with on thermoplastic resin with special selection component and the surface that is attached to integratedly this aluminium alloy shape thing with injection molding and consist of, in other words, the operation of the metal of this complex (aluminium alloy) shape thing and the composition of resin shape thing have all been becomed privileged to be limited, and relatively comparatively complicated, preparation method and the application of complex are restricted, the service efficiency and the range of application that are unfavorable for this metal shell, especially use the aqueous solution of special selection more not meet present environmental requirement, therefore can be considered the shortcoming of above-mentioned these metal shell article.
Disclosed a kind of correlation technique of resin-coated metal sheet for another domestic application for a patent for invention number 85100575 (notification numbers 404888) " the high clarity resin-coated metal sheet with excellent processing adhesion ", it is as substrate take metallic plate, at least on this substrate unilateral, by substrate-side is sequentially laminated dope layer arranged, the thick denaturing acrylamide resin bed of 5～100 μ m that polypropylene copolymer 100～20 weight portions and polypropylene 100～0 weight portions consist of, style and/or overall printed layer, adhesion agent layer, the polyester based resin film (seeing its claim 1) that 5～100 μ m are thick; Or by the substrate-side thick polyester based resin film (seeing its claim 2) of denaturing acrylamide resin bed, adhesion agent layer, 5～100 μ m that sequentially laminated 5～100 μ m that have dope layer, style and/or overall printed layer, polypropylene copolymer 100～20 weight portions and polypropylene 100～0 weight portions to consist of are thick; Or by the substrate-side thick transparent polyester based resin film (seeing its claim 3) of denaturing acrylamide resin bed, adhesion agent layer, 5～100 μ m that sequentially laminated 5～100 μ m that have dope layer, polypropylene copolymer 100～20 weight portions and polypropylene 100～0 weight portions to consist of are thick; Or by substrate-side is sequentially laminated dope layer, sex change olefin layer that 5～100 μ m are thick, adhesion agent layer, transparent polyester based resin film person (claim 4) that 5～100 μ m are thick arranged.Yet, in this invention structure by substrate-side sequentially the composition of laminated resin-coated layer all becomed privileged and limited, and main purpose is that this resin-coated metal sheet has high clarity, and the profile of this metallic plate is restricted, and is unfavorable for the application of made metal shell.
Domestic application for a patent for invention number 86106332 (notification numbers 434145) " possess the coated with resins sheet metal than high-resolution reflectivity and good work tackness " and have disclosed a kind of correlation technique of coated with resins sheet metal for another example, it comprises: as the sheet metal of bottom chip, arithmetic mean of instantaneous value deviation amplitude (Ra) numerical value of its roughness is between 0 micron and 10 microns; Transparent soft resin layer, it comprises unhardened mixing kenel resin bed, the coating coat of mylar, or vistanex; The following layer that comprises pigment; Have the two sides through the transparent resin film of gloss finish, wherein at least one sheet metal surface is colored layer, soft resin layer, following layer and hyaline layer covering, and each layer is sequentially to cover to transparent resin film from the sheet metal side.Yet, in this invention structure by the sheet metal side sequentially the composition of laminated resin-coated layer all becomed privileged and limited, and main purpose is that this resin-coated metal sheet has high clarity, and the profile of this metallic plate is restricted relatively, is unfavorable for the application of made metal shell.
For another example domestic application for a patent for invention number 093119015 (certificate number I280190) " case of electronic device metal plate forming process and structure thereof ", it is improved for aforesaid application for a patent for invention number 86106332 (notification numbers 434145) and application for a patent for invention number 85100575 (notification numbers 404888), it discloses a kind of correlation technique that the aluminium alloy base plate of skin membrane is set, its method comprises at least: one " coating solid " step, be in an at least one side surface coating one deck solid by the made metal substrate of aluminium alloy, and this solid have metal dust; One " Baking out " step heats the metal substrate of this coating solid, makes this solid suitably softening; One " roll extrusion " step, via the roller of heating that one skin membrane roll extrusion is laminated on this solid, wherein this skin membrane is by at least one polyvinyl chloride layer, a following layer, a polyester layer stacking being combined into sequentially, and following layer has metal dust; One " cooling forming " step makes this skin membrane and metal substrate be able to adherence and is combined.Yet, by at least one polyvinyl chloride layer, a following layer, a polyester layer stacking being combined into sequentially by the composition of the laminated skin membrane of Al-alloy metal substrate one side surface in this invention structure, therefore this skin membrane has been becomed privileged and has been limited, the profile that this metal substrate is presented is restricted, and is unfavorable for the application of made metal shell (being the case of electronic device metallic plate).
Domestic new patent application number 093210282 (certificate number M261368) " electronic device casing metal plate structure " is the new patent invention of structure among aforementioned application for a patent for invention number 093119015 (the certificate number I280190) for another example.Yet this invention structure also exists as the skin membrane of its application for a patent for invention number 093119015 has been becomed privileged the shortcoming that limits.
For another example domestic new patent application number 097208521 (certificate number M345706) " composition metal plate structure " disclosed comprise metal substrate, be coated on this metal substrate and thermoplastic compound resin glue-line, and with a running roller roll extrusion laminated on this compound resin glue-line metal decking and this metal decking is combined with the metal substrate adherence.Yet two lateral surfaces one of this invention structure are that metal decking one is metal substrate, so exist two lateral surfaces to be becomed privileged the shortcoming that limits.
Domestic new patent application number 096215339 (certificate number M328384) " environment protection type metal-covering structure " has disclosed the correlation technique of a type metal-covering structure for another example, and it comprises at least: a metal substrate; At least one side surface and the heating of coating the aforementioned metal substrate make it suitably softening adhesion agent layer; And by a polyurethane bottom and the polyurethane surface layer stacking skin membrane that is combined into sequentially, make its laminated then cooling on aforementioned adhesion agent layer with a roller roll extrusion, this skin membrane is combined with the metal substrate adherence.Yet, the composition of the skin membrane in this invention structure is by a polyurethane bottom and polyurethane surface layer stacking being combined into sequentially, therefore this skin membrane is defined by particularization, and profile or sense of touch that this metal substrate is presented are restricted relatively, are unfavorable for the application of made metal shell.
In sum, really have some shortcomings in the prior art of composite board, the present invention effectively solves for the shortcoming of above-mentioned prior art.
Summary of the invention
The composite board that the object of the present invention is to provide a kind of metal substrate to be combined with outer finishing coat, it is sequentially comprised by metal substrate to outer finishing coat: a metal substrate, one the one TPR adhesion layer, one the 2nd TPR adhesion layer and an outer finishing coat, wherein:
This metal substrate is the sheet metal with suitable thickness, and its surface has the thin shrinkage pool of several intimate uniform folds, and this thin shrinkage pool is spontaneous in its surface in the moulding manufacturing process of this metal substrate;
The one TPR adhesion layer is to be made of the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize, its thickness is 400-500 μ m, it is to be fitted on the side surface of this metal substrate by roller or dull and stereotyped heating pressuring method hot pressing, and its segment thickness infiltrates in hot pressing is fitted in described several thin shrinkage pools on this metallic substrate surfaces;
The 2nd TPR adhesion layer is to be made of the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize, and its thickness is 400-500 μ m, and it pastes on a side surface of this outer finishing coat;
This outer finishing coat is that a decoration is used thin layer, has the pore of several intimate uniform folds on its surface, and these pores are spontaneous on the surface in the moulding manufacturing process of this outer finishing coat;
Wherein, this metal substrate and outer finishing coat utilize the hot pressing bonding process and mutually hot pressing fit to form a composite board;
Wherein, when this metal substrate and outer finishing coat when carrying out the hot pressing bonding process, TPR adhesion layer between the two is combined with the simultaneously mutual hot melt of the 2nd TPR adhesion layer, and the segment thickness of the 2nd TPR adhesion layer infiltrates in several existing on this outer finishing coat surface pores simultaneously, so that outer finishing coat closely sticks together on a side surface of metal substrate by the 2nd TPR adhesion layer and a TPR adhesion layer, and reach the degree of sticking together of allowing deep processing and not peeling off.
Wherein, this metal substrate is aluminium alloy plate.
This outer finishing coat is bed of cloth, and the hair of its cotton by natural fiber such as string, fiber crops or animal origin, silk consists of, or is made of staple fibre such as nylon, polyester fiber, acryl fiber.
This outer finishing coat is leather layer, and it is made of natural leather such as sheepskin, ox-hide, or is made of PU, PVC or PU and the synthetic skin of PVC.
This outer finishing coat is the bamboo wood layer that the bamboo chip by the shape of chipping consists of.
This outer finishing coat is the lumber layer that the wood chip by the shape of chipping consists of.
The one TPR adhesion layer thickness 400-500 μ m (10
-6M) 10% part in, namely the thickness of about 40-50 μ m infiltrates in hot pressing is fitted in described several thin shrinkage pools on this metallic substrate surfaces.
Another object of the present invention provides a kind of method for making of described composite board, comprises the following step:
Metal substrate with suitable thickness is provided, and naturally has intimate uniform fold several thin shrinkage pools in its surface because of its its shaping process on the surface of this metal substrate;
By roller or dull and stereotyped heating pressuring method, hot pressing a layer thickness is the TPR adhesion layer of 400-500 μ m on a side surface of this metal substrate, this TPR adhesion layer is to be made of the thermoplastic rubber film that synthesizes with butadiene-styrene block copolymer and hydrocarbon Petropols, and the segment thickness of a TPR adhesion layer about 10% (about 40-50 μ m) is infiltrated in hot pressing in several existing on the metallic substrate surfaces thin shrinkage pools;
Outer finishing coat with suitable thickness is provided, and naturally has intimate uniform fold several pores in its surface because of its forming process on the surface of this outer finishing coat;
By the mode of heating of roller, pasting thickness on a surface of this outer finishing coat is 400-500 μ m (10
-6M) the 2nd TPR adhesion layer, this TPR adhesion layer are to be made of the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize;
Again to said metal substrates and outer finishing coat, carry out the hot pressing bonding process one time, so that this metal substrate and outer finishing coat by each upper first and second set TPR adhesion layer in surface mutually hot pressing fit, and make the 2nd TPR adhesion layer in this hot pressing bonding process, infiltrate in several existing pores of this outer finishing coat surface and the simultaneously TPR adhesion layer adherence on metal substrate is combined;
After cooling, form the integral type composite board with metal substrate and outer finishing coat.
Wherein, this metal substrate is aluminium alloy plate.
The material of this outer finishing coat comprises a kind of in the following cohort: bed of cloth is as being made of natural or staple fibre, leather layer is as being made of the synthetic skin of natural or PU/PVC, and the bamboo wood layer is made of the bamboo chip of the shape of chipping or lumber layer is made of the wood chip of the shape of chipping.
This hot pressing bonding process further comprises a Baking out operation, in order to a TPR adhesion layer set on this metallic substrate surfaces is carried out the Baking out operation, makes a TPR adhesion layer be heated to about 130 ℃, makes it suitably to soften to be beneficial to the operation of fitting.
This hot pressing bonding process further comprises a Baking out operation, in order to the 2nd set on this outer finishing coat surface TPR adhesion layer is carried out the Baking out operation, so that the 2nd TPR adhesion layer is heated to about 130 ℃, makes it suitably to soften to be beneficial to paste operation.
This hot pressing bonding process further utilizes the roller of heating, its temperature is maintained at about 140 ℃, in order to outer finishing coat is laminated on a TPR adhesion layer of this metal substrate with roll extrusion by its lip-deep the 2nd TPR adhesion layer, so that outer finishing coat is combined with the metal substrate adherence.
Composite board of the present invention and method for making thereof, because the 2nd TPR adhesion layer can infiltrate in the existing pore in this outer finishing coat surface and the simultaneously firm adherence of a TPR adhesion layer on metal substrate is combined and is difficult for peeling off by this hot pressing bonding process, make the composite board of institute's moulding need carrying out deep processing operations for forming such as deep-draw with design, stretch, cut etc., in order to make the hull shape thing that has strength advantage and beautiful decoration advantage concurrently, avoid sticking together in the prior art the not good and normal relatively limited shortcoming of outer finishing coat material therefor of effect and Forming Quality.
Composite board of the present invention and method for making thereof, but because this outer finishing coat choice for use cloth cover, veneer or synthetic veneer, natural or synthetic resin fiber surface layer etc., make this composite board or formed hull shape thing be had various outward appearance style and/or sense of touch, the variation of increase product appearance and consumer's is selective, be conducive to improve value and the market competitiveness of product, and can avoid in the prior art material difference along with outer finishing coat namely must develop in addition the puzzlement that the different preparation method of a cover and equipment just can be finished composite board, reach the production efficiency height, easily mass production, but deep-draw processing and the good practical function of Forming Quality keyholed back plate.
Description of drawings
Fig. 1 is composite board preparation method's of the present invention schematic flow sheet;
Fig. 2 is section (amplification) schematic diagram of plywood sheet structure of the present invention;
Fig. 3 utilizes composite board of the present invention to form the front perspective view of a hull shape thing through the punch forming machining of extending;
Fig. 4 is that the back of the body of Fig. 3 is looked schematic perspective view.
Description of reference numerals: 1-composite board; 2-hull shape thing; The 10-metal substrate; The 11-surface; The thin shrinkage pool of 12-; 20-the one TPR adhesion layer; The 21-interface; The 30-outer finishing coat; The 31-surface; The 32-pore; 40-the 2nd TPR adhesion layer; The 41-interface; The 50-dotted line.
The specific embodiment
Below in conjunction with accompanying drawing, be described in more detail with other technical characterictic and advantage the present invention is above-mentioned.
With reference to figure 1, it is manufacture method flow chart schematic diagram of the present invention.The method for making of composite board 1 of the present invention mainly comprises the following step:
On at least one side surface of this metal substrate 10, by roller or the dull and stereotyped about 400-500 μ of heating pressuring method hot pressing a layer thickness m (μ m=10
-6M) a TPR adhesion layer 20, this TPR is the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols, and making the segment thickness of a TPR adhesion layer 20,10% about 40-50 μ m can infiltrate in several existing on the metallic substrate surfaces thin shrinkage pools according to appointment;
Outer finishing coat 30 with suitable thickness is provided; This outer finishing coat 30 comprises but is not restricted to a kind of in the following cohort: as by bed of cloth natural or that staple fibre consists of, as synthesizing the leather layer that skin consists of by natural or PU/PVC, the bamboo wood layer that is consisted of by the bamboo chip of the shape of chipping or the lumber layer that consisted of by the wood chip of the shape of chipping etc., and naturally have with the general moulding production process of this outer finishing coat 30 on the surface of this outer finishing coat 30 and can be considered several pores that are close to uniformly dispersing;
On the surface of the wish combination of this outer finishing coat 30, by roller heating but do not pressurize or the mode that only adds a little pressure pastes the 2nd TPR adhesion layer 40 of the about 400-500 μ of thickness m, and the 2nd TPR adhesion layer 40 is not infiltrated in several surperficial existing pores of outer finishing coat;
Again for said metal substrates 10 and outer finishing coat 30, carry out the hot pressing bonding process one time, so that this metal substrate 10 and outer finishing coat 30 by upper set first and second TPR adhesion layer 20 in each surface, 40 and mutually hot pressing fit, and make the 2nd TPR adhesion layer 40 infiltrate in several existing pores of these outer finishing coat 30 surfaces and a simultaneously TPR adhesion layer 20 firm adherences on metal substrate 10 are combined in this hot pressing bonding process punching;
After cooling, namely form the integral type composite board 1 with metal substrate 10 and outer finishing coat 30, as shown in Figure 2.
Via above-mentioned method for making of the present invention, since the 2nd TPR adhesion layer 40 can infiltrate in this hot pressing bonding process in several existing on these outer finishing coat 30 surfaces pores and simultaneously with metal substrate 10 on a TPR adhesion layer 20 firm underground heat melt adherence and be combined into one, so made composite board 1 can the combination between metal substrate 10 and outer finishing coat 30 keep quite good adherence, and after entity test, prove the follow-up deep processing operations for forming such as the deep-draw that are enough to bear various different modes, stretch, cut etc.; Therefore, composite board 1 of the present invention can need to carry out the deep processing operations for forming with design, supply in order to make the hull shape thing 2 that has strength advantage and beautiful decoration advantage concurrently, shown in Fig. 3,4, thereby avoid sticking together in the prior art effect and Forming Quality is not good and the normal relatively limited shortcoming of outer finishing coat material therefor.
Especially, method for making of the present invention is compared with these prior aries, and method for making of the present invention more can meet present environmental requirement.Method for making of the present invention is to utilize upward several thin shrinkage pools of institute's self-assembling formation and intimate uniformly dispersing in its moulding production process of these metal substrate 10 surfaces, so that the segment thickness of a TPR adhesion layer 20 can directly infiltrate in these thin shrinkage pools in heat-press step, therefore do not utilize any special aqueous solution or any concerned process steps that metal substrate is immersed in the special aqueous solution in the method for the present invention, thereby make and have the thermoplastic resin molded of special composition and stick together on the surface at this metal substrate, such as Chinese patent ZL02805359.1 first to form or to cover several recesses with the degree of depth to a certain degree or internal diameter in metallic substrate surfaces, ZL200380102886.0, the correlation technique that the prior art such as ZL200380104500.X and ZL200680046075.7 discloses.
In the said method, before surperficial hot pressing the one TPR adhesion layer 20 of metal substrate 10, can need for the surface state of this metal substrate 10, and take first a purified treatment step, this purified treatment step comprise and be not restricted to degreasing, brute force is scrubbed etc., main purpose is to make the working surface of this metal substrate 10 to remain on to a certain degree clean state, avoiding that the heat pressing operation program of a follow-up TPR adhesion layer 20 is produced harmful effect, reach the good effect of closely following between the surface of a TPR adhesion layer 20 and metal substrate 10 thereby make.
In the said method, make outer finishing coat 30 in employed hot pressing bonding process is combined in metal substrate 10 adherences, the following operation that further can comprise and not limit: as before carrying out the hot pressing bonding process, carry out first a Baking out operation, carry out the Baking out operation in order to a TPR adhesion layer 20 set on the surface to this metal substrate 10, so that a TPR adhesion layer 20 can be heated to about 130 ℃ and suitably softening, be beneficial to the 2nd set on the surface with outer finishing coat 30 TPR adhesion layer 40 and carry out the hot pressing bonding process; Also can further carry out another Baking out operation, carry out the Baking out operation in order to the 2nd set on the surface to this outer finishing coat 30 TPR adhesion layer 40, so that the 2nd TPR adhesion layer 40 can be heated to about 130 ℃ and suitably softening, be beneficial to a TPR adhesion layer 20 set on the surface with metal substrate 10 and carry out the hot pressing bonding process.
In the said method, can utilize the roller of a heating to carry out this hot pressing bonding process, and the temperature of this roller can be maintained at about 140 ℃, on the surface with the outer finishing coat 30 laminated TPR adhesion layer 20 in this metal substrate 10 of roll extrusion by the 2nd TPR adhesion layer 40, so that outer finishing coat 30 and metal substrate 10 form integral type composite board 1 by first and second TPR adhesion layer 20,40 fusion characteristic.
With reference to figure 2, it is the structural profile schematic diagram of composite board 1 of the present invention.The structure of integral type composite board 1 of the present invention sequentially comprises: the major parts such as a metal substrate 10, one the one TPR adhesion layer 20, one the 2nd TPR adhesion layer 40 and an outer finishing coat 30.
This metal substrate 10 is can be in order to the metal unit material of the hull shape thing 2 that consists of an electronic installation, this hull shape thing 2 is shown in Fig. 3,4, comprising and be not restricted to the housing of the 3C Products such as computer (computer) product, communication (communication) product or consumer (consumer) product, generally is to utilize the good metallic plate of light weight intensity such as aluminium alloy plate; Basically have several thin shrinkage pools 12 on the surface 11 of this metal substrate 10 (for asking obvious, shrinkage pool 12 is to amplify expression among the figure) and can be considered and be close to uniformly dispersing or cover on the surface 11, and described thin shrinkage pool 12 be in the forming process of common metal substrate 10 such as calendering forming processing and spontaneous from the teeth outwards, be not to be to utilize the special aqueous solution of any process or anyly metal substrate 10 is immersed in the concerned process steps of the special aqueous solution and forms.
The one TPR adhesion layer 20 is to consist of with the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize, and the ratio of its material composition can be different, such as the TPU.TPE film, and the about 400-500 μ of its thickness m (1 μ m=10
-6M), its be via roller or dull and stereotyped heating pressuring method hot pressing on the surface of at least one side of this metal substrate 10 and be combined into one with this metal substrate 10, and the segment thickness of a TPR adhesion layer 20,10% of original thickness about 40-50 μ m according to appointment, can in operation is fitted in hot pressing, infiltrate through on the surface 11 of metal substrate 10 in existing these several thin shrinkage pool 12, by increasing the tack strength between a TPR adhesion layer 20 and this metal substrate 10 in case in deep-draw processing, peel off or damaged.And the lateral surface of a TPR adhesion layer 20 represents with interface 21.
The 2nd TPR adhesion layer 40 is to consist of with the synthetic thermoplastic rubber film of butadiene-styrene block copolymer and hydrocarbon Petropols, and the material of itself and a TPR adhesion layer 40 can be identical, or material composition is identical but mixed proportion different, such as the TPU.TPE film; The in addition about 400-500 μ of the 2nd TPR adhesion layer 40 thickness m, it is by the heating of roller but does not pressurize or the mode that only adds a little pressure pastes on the surface 31 of this outer finishing coat 30, but in pasting operation, because of the heating of roller but do not pressurize or only add a little pressure, the 2nd TPR adhesion layer 40 is not infiltrated in several existing on the surface 31 of outer finishing coat 30 pores 32, namely metal substrate 10 and outer finishing coat 30 are before carrying out the hot pressing bonding process, and the 2nd TPR adhesion layer 40 does not infiltrate in several existing on the surface 31 of outer finishing coat 30 pores 32.And the lateral surface of the 2nd TPR adhesion layer 40 represents with interface 41.
In addition, composite board 1 shown in Figure 3 is through the article shaped after the hot pressing bonding process, this moment this metal substrate 10 and outer finishing coat 30 by first and second TPR adhesion layer 20,40 and mutually hot pressing fit, namely mutually hot melt combination between first and second TPR adhesion layer 20,40, therefore so can't keep again or indicate first and second TPR adhesion layer 20,40 original interfaces 21/41 among Fig. 3, in Fig. 3, represent as-welded between original interface 21/41 with the dotted line 50 of two appropriate intervals in addition.
This outer finishing coat 30 comprises and is not restricted to a kind of in the following cohort: a bed of cloth, and the wool of its cotton by natural fiber such as string, fiber crops etc. or animal origin, silk etc., or staple fibre such as nylon, polyester fiber, acryl fiber consist of; One leather layer, it is made of natural skin or the synthetic skin of PU/PVC; One bamboo wood layer, its bamboo chip by the shape of chipping consists of; Or a lumber layer, its wood chip by the shape of chipping consists of etc.; This outer finishing coat 30 can need to specify and processing out of the ordinary such as the subscriber with using, thereby has various outward appearance style or sense of touch; In addition, naturally have several pores 32 that can be considered intimate uniformly dispersing along with the moulding production process of this outer finishing coat 30 on the surface 31 of this outer finishing coat 30, such as the mesh of natural or staple fibre or the pore of natural skin.Therefore, when metal substrate 10 and outer finishing coat 30 when carrying out the hot pressing bonding process, the 2nd TPR adhesion layer 40 can infiltrate in several existing on the surface 31 of outer finishing coat 30 pores 32 simultaneously, so that outer finishing coat 30 can be by the 2nd TPR adhesion layer 40 and a TPR adhesion layer 20 and closely stick together on a side surface of metal substrate 10, and reach the degree of closely sticking together of allowing deep processing and not peeling off.
Now by following each embodiment (wherein metal substrate 10 is all aluminium alloy plate, but outer finishing coat 30 is unlike material), further specify the structure of composite board 1 of the present invention and the action and efficacy that can reach thereof:
＜embodiment 1 〉
The composite board 1 of present embodiment comprises:
Outer finishing coat 30 is for being the bed of cloth of 0.3mm take institute's formation thickness such as the wool of the cotton of natural fiber such as string, fiber crops etc. or animal origin, silks, and upper the 2nd set TPR adhesion layer 40 in its surface consists of the about 400-500 μ of thickness m for the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols;
After the hot pressing bonding process, the thickness of the composite board 1 of institute's moulding is 1.1mm;
Found that, the peel strength adherence of present embodiment is 5 kilograms every square centimeter, serve as reasons-40 ℃ to 85 ℃ and 85 ℃ to-40 ℃ per minutes of environmental testing adherence heats up or lowers the temperature 1 ℃ and through 4 circulations, the hull shape thing that forms with this composite board is shown in Fig. 3,4, and wherein this outer finishing coat 30 is not peeled off with aluminium alloy plate 10.
＜embodiment 2 〉
The composite board 1 of present embodiment comprises:
Outer finishing coat 30 for take staple fibre such as nylon, polyester fiber, the acryl fiber is consisted of and thickness as the bed of cloth of 0.3mm, and upper the 2nd set TPR adhesion layer 40 in its surface consists of the about 400-500 μ of thickness m for the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols;
After the hot pressing bonding process, the thickness of the composite board 1 of institute's moulding is 1.1mm;
Found that, the peel strength adherence of present embodiment is 5 kilograms every square centimeter, serve as reasons-40 ℃ to 85 ℃ and 85 ℃ to-40 ℃ per minutes of environmental testing adherence heats up or lowers the temperature 1 ℃ and through 4 circulations, the hull shape thing that forms with this composite board is shown in Fig. 3,4, and wherein this outer finishing coat 30 is not peeled off with aluminium alloy plate 10.
＜embodiment 3 〉
The composite board 1 of present embodiment comprises:
Outer finishing coat 30 is for being consisted of take the natural leather sheepskin and thickness is the leather layer of 0.4mm, and upper the 2nd set TPR adhesion layer 40 in its surface consists of the about 400-500 μ of thickness m for the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols;
After the hot pressing bonding process, the thickness of the composite board 1 of institute's moulding is 1.2mm;
Found that, the peel strength adherence of present embodiment is 5 kilograms every square centimeter, serve as reasons-40 ℃ to 85 ℃ and 85 ℃ to-40 ℃ per minutes of environmental testing adherence heats up or lowers the temperature 1 ℃ and through 4 circulations, the hull shape thing that forms with this composite board is shown in Fig. 3,4, and wherein this outer finishing coat 30 is not peeled off with aluminium alloy plate 10.
＜embodiment 4 〉
The composite board 1 of present embodiment comprises:
Outer finishing coat 30 is the leather layer of 0.5mm for synthesize skin formation and thickness take PU/PVC, and upper the 2nd set TPR adhesion layer 40 in its surface consists of the about 400-500 μ of thickness m for the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols;
After the hot pressing bonding process, the thickness of the composite board 1 of institute's moulding is 1.3mm;
Found that, the peel strength adherence of present embodiment is 5 kilograms every square centimeter, serve as reasons-40 ℃ to 85 ℃ and 85 ℃ to-40 ℃ per minutes of environmental testing adherence heats up or lowers the temperature 1 ℃ and through 4 circulations, the hull shape thing that forms with this composite board is shown in Fig. 3,4, and wherein this outer finishing coat 30 is not peeled off with aluminium alloy plate 10.
＜embodiment 5 〉
The composite board 1 of present embodiment comprises:
Outer finishing coat 30 consists of for the bamboo chip take the shape of chipping and thickness is the bamboo wood layer of 0.4mm, and upper the 2nd set TPR adhesion layer 40 in its surface consists of the about 400-500 μ of thickness m for the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols;
After the hot pressing bonding process, the thickness of the composite board 1 of institute's moulding is 1.2mm;
Found that, the peel strength adherence of present embodiment is 5 kilograms every square centimeter, serve as reasons-40 ℃ to 85 ℃ and 85 ℃ to-40 ℃ per minutes of environmental testing adherence heats up or lowers the temperature 1 ℃ and through 4 circulations, the hull shape thing that forms with this composite board is shown in Fig. 3,4, and wherein this outer finishing coat 30 is not peeled off with aluminium alloy plate 10.
＜embodiment 6 〉
The composite board 1 of present embodiment comprises:
Outer finishing coat 30 consists of for the ply take the shape of chipping and thickness is the bamboo wood layer of 0.4mm, and upper the 2nd set TPR adhesion layer 40 in its surface consists of the about 400-500 μ of thickness m for the thermoplastic rubber film that is synthesized by butadiene-styrene block copolymer and hydrocarbon Petropols;
After the hot pressing bonding process, the thickness of the composite board 1 of institute's moulding is 1.2mm;
Found that, the peel strength adherence of present embodiment is 5 kilograms every square centimeter, serve as reasons-40 ℃ to 85 ℃ and 85 ℃ to-40 ℃ per minutes of environmental testing adherence heats up or lowers the temperature 1 ℃ and through 4 circulations, the hull shape thing that forms with this composite board is shown in Fig. 3,4, and wherein this outer finishing coat 30 is not peeled off with aluminium alloy plate 10.
The above only is preferred embodiment of the present invention, only is illustrative for the purpose of the present invention, and nonrestrictive.Those skilled in the art is understood, and can carry out many changes to it in the spirit and scope that claim of the present invention limits, revise, even equivalence, but all will fall within the scope of protection of the present invention.
Claims (18)
1. the composite board that metal substrate is combined with outer finishing coat is characterized in that, it is sequentially comprised by metal substrate to outer finishing coat: a metal substrate, one the one TPR adhesion layer, one the 2nd TPR adhesion layer and an outer finishing coat, wherein:
This metal substrate is the sheet metal with suitable thickness, and its surface has the thin shrinkage pool of several intimate uniform folds, and these thin shrinkage pools are spontaneous in its surface in the moulding manufacturing process of this metal substrate;
The one TPR adhesion layer is to be made of the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize, its thickness is 400-500 μ m, it is to be fitted on the side surface of this metal substrate by roller or dull and stereotyped heating pressuring method hot pressing, and its segment thickness infiltrates in hot pressing is fitted in described several thin shrinkage pools on this metallic substrate surfaces;
The 2nd TPR adhesion layer is to be made of the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize, and its thickness is 400-500 μ m, and it pastes on a side surface of this outer finishing coat;
This outer finishing coat is that a decoration is used thin layer, has the pore of several intimate uniform folds on its surface, and these pores are spontaneous on the surface in the moulding manufacturing process of this outer finishing coat;
Wherein, this metal substrate and outer finishing coat utilize the hot pressing bonding process and mutually hot pressing fit to form a composite board;
Wherein, when this metal substrate and outer finishing coat when carrying out the hot pressing bonding process, TPR adhesion layer between the two is combined with the simultaneously mutual hot melt of the 2nd TPR adhesion layer, and the segment thickness of the 2nd TPR adhesion layer infiltrates in several existing on this outer finishing coat surface pores simultaneously, so that outer finishing coat closely sticks together on a side surface of metal substrate by the 2nd TPR adhesion layer and a TPR adhesion layer, and reach the degree of sticking together of allowing deep processing and not peeling off.
2. composite board as claimed in claim 1 is characterized in that, this metal substrate is aluminium alloy plate.
3. composite board as claimed in claim 1 is characterized in that, this outer finishing coat is bed of cloth, and it is made of natural fiber.
4. composite board as claimed in claim 3 is characterized in that, described natural fiber is hair, the silk of cotton, fiber crops or the animal origin of string.
5. composite board as claimed in claim 1 is characterized in that, this outer finishing coat is bed of cloth, and it is made of staple fibre.
6. composite board as claimed in claim 5 is characterized in that, described staple fibre is nylon, polyester fiber, acrylic fiber.
7. composite board as claimed in claim 1 is characterized in that, this outer finishing coat is leather layer, and it is made of natural leather.
8. composite board as claimed in claim 7 is characterized in that, described natural leather is sheepskin, ox-hide.
9. composite board as claimed in claim 1 is characterized in that, this outer finishing coat is leather layer, and it is made of PU, PVC or PU and the synthetic skin of PVC.
10. composite board as claimed in claim 1 is characterized in that, this outer finishing coat is the bamboo wood layer, and its bamboo chip by the shape of chipping consists of.
11. composite board as claimed in claim 1 is characterized in that, this outer finishing coat is lumber layer, and its wood chip by the shape of chipping consists of.
12. composite board as claimed in claim 1 is characterized in that, 10% part among the TPR adhesion layer thickness 400-500 μ m, and namely the thickness of 40-50 μ m infiltrates in hot pressing is fitted in described several thin shrinkage pools on this metallic substrate surfaces.
13. the method for making of the composite board that a metal substrate is combined with outer finishing coat is characterized in that, in order to make each described composite board among the claim 1-12, comprises the following step:
Metal substrate with suitable thickness is provided, and naturally has intimate uniform fold several thin shrinkage pools in its surface because of its forming process on the surface of this metal substrate;
By roller or dull and stereotyped heating pressuring method, hot pressing a layer thickness is the TPR adhesion layer of 400-500 μ m on a side surface of this metal substrate, this TPR adhesion layer is to be made of the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize, and the segment thickness of a TPR adhesion layer 10% is infiltrated in hot pressing in several existing on the metallic substrate surfaces thin shrinkage pools;
Outer finishing coat with suitable thickness is provided, and naturally has intimate uniform fold several pores in its surface because of its forming process on the surface of this outer finishing coat;
By the mode of heating of roller, pasting thickness on a surface of this outer finishing coat is the 2nd TPR adhesion layer of 400-500 μ m, and this TPR adhesion layer is to be made of the thermoplastic rubber film that butadiene-styrene block copolymer and hydrocarbon Petropols synthesize;
Again to said metal substrates and outer finishing coat, carry out the hot pressing bonding process one time, so that this metal substrate and outer finishing coat by each upper first and second set TPR adhesion layer in surface mutually hot pressing fit, and make the 2nd TPR adhesion layer in this hot pressing bonding process, infiltrate in several existing pores of this outer finishing coat surface and the simultaneously TPR adhesion layer adherence on metal substrate is combined;
After cooling, form the integral type composite board with metal substrate and outer finishing coat.
14. the method for making of composite board as claimed in claim 13 is characterized in that, this metal substrate is aluminium alloy plate.
15. the method for making of composite board as claimed in claim 13, it is characterized in that, the material of this outer finishing coat comprises a kind of in the following cohort: by bed of cloth natural or that staple fibre consists of, the leather layer that is consisted of by the synthetic skin of natural or PU/PVC, the bamboo wood layer that is consisted of by the bamboo chip of the shape of chipping or the lumber layer that is consisted of by the wood chip of the shape of chipping.
16. the method for making of composite board as claimed in claim 13, it is characterized in that, this hot pressing bonding process further comprises a Baking out operation, in order to a TPR adhesion layer set on this metallic substrate surfaces is carried out the Baking out operation, make a TPR adhesion layer be heated to 130 ℃, make it suitably to soften to be beneficial to the operation of fitting.
17. the method for making of composite board as claimed in claim 13, it is characterized in that, this hot pressing bonding process further comprises a Baking out operation, in order to the 2nd set on this outer finishing coat surface TPR adhesion layer is carried out the Baking out operation, so that the 2nd TPR adhesion layer is heated to 130 ℃, make it suitably to soften to be beneficial to paste operation.
18. the method for making of composite board as claimed in claim 13, it is characterized in that, this hot pressing bonding process further utilizes the roller of heating, its temperature remains on 140 ℃, in order to outer finishing coat is laminated on a TPR adhesion layer of this metal substrate with roll extrusion by its lip-deep the 2nd TPR adhesion layer, so that outer finishing coat is combined with the metal substrate adherence.
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| CN 201010118410 CN102189720B (en) | 2010-03-05 | 2010-03-05 | Composite board combining metal substrate and outer decoration layer and manufacturing method for composite board |
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| CN 201010118410 CN102189720B (en) | 2010-03-05 | 2010-03-05 | Composite board combining metal substrate and outer decoration layer and manufacturing method for composite board |
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| CN102189720B true CN102189720B (en) | 2013-10-16 |
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| KR101335272B1 (en) * | 2013-05-21 | 2013-11-29 | 주식회사 에스아이 플렉스 | Subsidiary for fpcb laminated attaching method |
| CN106132123A (en) * | 2016-08-26 | 2016-11-16 | 北京珠穆朗玛移动通信有限公司 | Shell for electronic equipment and preparation method thereof |
| CN110254023A (en) * | 2019-06-19 | 2019-09-20 | 福州索科特材料科技有限公司 | A kind of processing method of 3D hot press composite board |
| CN111394038B (en) * | 2020-04-30 | 2022-03-01 | 广州鹿山新材料股份有限公司 | Spraying-free glue for plastic uptake PVC decorative film and preparation method thereof, plastic uptake plate and preparation method thereof |
| CN114940012B (en) * | 2022-07-25 | 2022-10-25 | 宁波均胜群英汽车系统股份有限公司 | Process for manufacturing a molded article for vehicle interior trim |
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| KR100827916B1 (en) * | 2002-11-08 | 2008-05-07 | 다이세이 플라스 가부시끼가이샤 | Composite of aluminum alloy and resin composition and process for producing the same |
| CN1966258A (en) * | 2005-11-17 | 2007-05-23 | 宣德科技股份有限公司 | Surface covering and its producing method |
| CN201018717Y (en) * | 2007-03-09 | 2008-02-06 | 薪富欣业有限公司 | Housing |
| TWM328384U (en) * | 2007-09-12 | 2008-03-11 | Lien Chy Laminated Metal Co Ltd | Metal substrate adhered with environmentally friendly skin |
| CN101462384A (en) * | 2007-12-21 | 2009-06-24 | 深圳富泰宏精密工业有限公司 | Moulding product |
| CN201659721U (en) * | 2010-03-05 | 2010-12-01 | 铂邑科技股份有限公司 | Composite plate of metal base plate combined with external decoration layer |
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