CN101396888B - Metal composite board and preparation method thereof - Google Patents
Metal composite board and preparation method thereof Download PDFInfo
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- CN101396888B CN101396888B CN 200710152530 CN200710152530A CN101396888B CN 101396888 B CN101396888 B CN 101396888B CN 200710152530 CN200710152530 CN 200710152530 CN 200710152530 A CN200710152530 A CN 200710152530A CN 101396888 B CN101396888 B CN 101396888B
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Abstract
The invention discloses a metal composite board, comprising metal substrate, as well as a chemical conversion treatment layer and one or more layer of resin bed which are sequentially attached on the surface of the metal substrate; wherein, the resin bed layer is a layer of polyolefin resin grafted by maleic anhydride, or a layer of blending polyolefin resin grafted by other resins or the maleic anhydride, and the other resins are polycarbonate, polycaprolactam, polyolefin, and polyethylene glycol terephthalate or polybutylene terephthalate. The invention also discloses a preparing method of the metal composite board. Both the processing adhesiveness and the impact work resistance of the metal composite board provided by the invention are excellent.
Description
Technical field
The present invention relates to a kind of composite metal plate, also relate to a kind of preparation method of this composite metal plate.
Background technology
At present, disclosed plastics clad with metal foil technology is that resin molding with thermoplastic resin covers on the surface treated sheet metal.The corrosion resistance of the sheet metal of the coated with resin that obtains thus, electrical insulating property and punching performance are excellent, therefore be used widely, building interiors such as external packing, the three-ply board furniture processed that is used for family's electrical articles such as capacitor, beverage can, AV machine or air conditioner cover, steel furniture, elevator upholstery, window materials, bathroom, unit wall material, unit bathroom ceiling material, dividing plate is decorated.
But the spendable resin material kind of these technology seldom, only can use polyvinyl chloride (PVC), PETG (PET), polybutylene terephthalate (PBT) (PBT), several resins of nylon (PA).This mainly is owing to be difficult to realize due to the strong bond of other non-polar resin such as ethene-1-octene copolymer (POE), polyethylene (PE), polypropylene (PP), Merlon (PC), acrylonitrile-butadiene-styrene copolymer (ABS) and PC/ABS alloy and metal base, and, in this technology, PVC, PET, PBT or PA resin are relatively poor to the adhesive force of metal.
CN1639387A discloses a kind of thermoplastic resin coating's aluminium sheet and preparation method thereof, this coating layer aluminium plate forms micropore matter anode oxide film at the single face of aluminium sheet at least, and form the processing film layer at this micropore matter anode oxide film, form thermoplastic resin at this film layer again and film.Described processing film layer is that coating is selected from a kind of in the middle of the organosilan coupling agent, epoxy resin, aliphatic acid, hydroxyl-substituted phenol and the film layer that forms.Described processing film layer is for to film through heat treated heat modification more than 250 ℃.Form the thermoplastic resin that thermoplastic resin is filmed at described processing film layer, can enumerate PETG, polybutylene terephthalate (PBT), the copolymer polyester resin that forms as a part of terephthalic acid (TPA) of the sour composition among ethylene glycol terephthalate or the mutual-phenenyl two acid bromide two alcohol ester with other acid substitution, or substitute terephthaldehyde's acetoacetic ester with other alcohol, the polyester resins such as copolymer polyester resin that the part ethylene glycol of terephthaldehyde's acid butyl ester forms, or mix the resin compound more than 2 kinds in this type of mylar, polyamide 6, polyamide 66, copolyamide 66-6, polyamide 6-10, polyamide 7, polyamide 12, the polyamide-based resin such as penylene dimethylamine between poly hexamethylene adipamide, polyethylene, polypropylene, the TPOs such as second the third copolyester and the polyolefin resin that carries out sour modification with maleic acid, Merlon, PEN, the thermoplastic resins such as fluorine-type resin.
Thermoplastic resin coating's aluminium sheet of this patent application and preparation method thereof has enlarged the kind of applicable thermoplastic resin.But formed processing film layer is to be selected from organosilan coupling agent, epoxy resin, aliphatic acid, the central a kind of film layer of hydroxyl-substituted phenol on thermoplastic resin coating's aluminium sheet.When adopting the organosilan coupling agent when processing film layer, with after having applied the aluminium sheet of processing film layer and being heated to heat-treating more than 250 ℃, organosilan coupling agent layer has the part efflorescence and becomes SiO
2, when material stands to be out of shape, process film layer and can peel off with the aluminium sheet generation, will affect like this processing tack and the shock-resistant processability of thermoplastic resin coating's plate.
When adopting epoxy resin, aliphatic acid or hydroxyl-substituted phenol as the processing film layer, be heated to more than 250 ℃ after the heat treatment having applied the aluminium sheet of processing film layer, although can improve between this film layer and the aluminium sheet this moment and and thermoplastic resin between bonding strength, but the elongation of the film layer tension failure after processing ability is relatively poor, therefore when this coating layer aluminium plate stands machining deformation, be easy to produce fracture, thereby the processing tack of thermoplastic resin coating's aluminium sheet and shock-resistant processability are relatively poor.
Summary of the invention
The object of the invention is to overcome processing tack and the relatively poor defective of shock-resistant processability of the coating layer aluminium plate of above-mentioned prior art, preferably composite metal plate and preparation method thereof of a kind of processing tack and shock-resistant processability is provided.
The invention provides a kind of composite metal plate, the chemical surface treatment layer that this composite metal plate comprises metal base and is attached to this metallic substrate surface, wherein, this composite metal plate also is included in one deck or which floor resin bed that forms on the metal base that is attached with the chemical surface treatment layer, described resin bed is the polyolefin resin layer of maleic anhydride graft, perhaps be the resin bed of the polyolefin blend of other resin and maleic anhydride graft, described other resin is Merlon, polycaprolactam, polyolefin, PETG or polybutylene terephthalate (PBT).
The present invention also provides a kind of preparation method of composite metal plate, the method comprises carries out chemical surface treatment with metal base, wherein, the method also is included in and forms one deck or which floor resin bed on the metal base that chemical surface treatment crosses, described resin bed is the polyolefin resin layer of maleic anhydride graft, perhaps be the resin bed of the polyolefin blend of other resin and maleic anhydride graft, described other resin is Merlon, polycaprolactam, polyolefin, PETG or polybutylene terephthalate (PBT).
Composite metal plate provided by the invention, the resin bed of the polyolefin blend of the polyolefin resin layer of maleic anhydride graft or other resin and maleic anhydride graft is formed directly on the metal base that is attached with the chemical surface treatment layer, and need not processing film layer of the prior art, at first be to have simplified preparation method.In addition, this resin bed can with the chemical surface treatment layer strong bond of metal base, thereby can obtain well to process tack and shock-resistant processability.
The specific embodiment
The chemical surface treatment layer that composite metal plate provided by the invention comprises metal base and is attached to this metallic substrate surface, wherein, this composite metal plate also is included in one deck or which floor resin bed that forms on the metal base that is attached with the chemical surface treatment layer, described resin bed is the polyolefin resin layer of maleic anhydride graft, perhaps be the resin bed of the polyolefin blend of other resin and maleic anhydride graft, described other resin is Merlon, polycaprolactam, polyolefin, PETG or polybutylene terephthalate (PBT).
According to composite metal plate provided by the invention, the resin that consists of composite metal plate resin bed of the present invention is not particularly limited, can be the various polyolefin of maleic anhydride graft, also can be the resin of the polyolefin blend of other resin and maleic anhydride graft, described other resin be Merlon, polycaprolactam, polyolefin, PETG or polybutylene terephthalate (PBT).
According to composite metal plate provided by the invention, described polyolefin can be various polyolefin, polypropylene for example, polyethylene (PE), polystyrene (PS), SBS (SBS), SB (SBC or K resin), ethene-1-octene copolymer (POE), ethylene propylene diene rubber (EPDM), EPM (EPM), acrylonitrile-butadiene-styrene copolymer (ABS) etc., wherein, polyethylene (PE) can be high density polyethylene (HDPE) or low density polyethylene (LDPE).
According to composite metal plate provided by the invention, the example of the resin of this resin bed can comprise, the polypropylene of maleic anhydride graft (PP-g-MAH), the polyacrylic blending resin (PP/PP-g-MAH) of polypropylene and maleic anhydride graft, the polyacrylic blending resin (PA6/PP-g-MAH) of polycaprolactam and maleic anhydride graft, the polyacrylic blending resin (PET/PP-g-MAH) of PETG and maleic anhydride graft, the ethene of maleic anhydride graft-1-octene copolymer (POE-g-MAH), the blending resin (PP/POE-g-MAH) of the ethene of polypropylene and maleic anhydride graft-1-octene copolymer, the blending resin (PA6/POE-g-MAH) of the ethene of polycaprolactam and maleic anhydride graft-1-octene copolymer, the acrylonitrile-butadiene-styrene copolymer of maleic anhydride graft (ABS-g-MAH), the blending resin of the acrylonitrile-butadiene-styrene copolymer of Merlon and maleic anhydride graft (PC/ABS-g-MAH), the polyethylene of maleic anhydride graft (PE-g-MAH), the poly blending resin (HDPE/PE-g-MAH) of high density polyethylene (HDPE) and maleic anhydride graft, the poly blending resin (LDPE/PE-g-MAH) of low density polyethylene (LDPE) and maleic anhydride graft, the poly blending resin (PC/PE-g-MAH) of Merlon and maleic anhydride graft, the poly blending resin (PBT/PE-g-MAH) of polybutylene terephthalate (PBT) and maleic anhydride graft, the SB of maleic anhydride graft (SBC or K resin), the blending resin (PA6/K-g-MAH) of the SB of polycaprolactam and maleic anhydride graft (SBC or K resin), the styrene-butadiene triblock copolymer (SBS-g-MAH) of maleic anhydride graft, the ethylene propylene diene rubber of maleic anhydride graft (EPDM-g-MAH), the blending resin (PA6/EPDM-g-MAH) of the ethylene propylene diene rubber of the blending resin of the ethylene propylene diene rubber of polyphenylene oxide and maleic anhydride graft (PPO/EPDM-g-MAH) and polycaprolactam and maleic anhydride graft.
According to composite metal plate provided by the invention, in the preferred case, the cantilever beam notched Izod impact strength of the resin of described resin bed is 100-650J/m.And consider that composite metal plate of the present invention will carry out the following process processing such as punch process, as carrying out the maleic anhydride group that bonding resin bed need to have enough grafting with metal, to guarantee the secure bond with the metal surface, enough toughness, tensile property, low degree of crystallinity and chemical resistance to be arranged also.Therefore, in the vistanex of described maleic anhydride graft, the percent grafting of maleic anhydride be preferably 0.1-15%, more preferably 0.5-10%, most preferably be 0.8-5%.
Term as used herein " percent grafting " expression, in the glycerol polymerization process, by the ratio of the monomer mass of grafting and resulting polymers gross mass (comprising the original copolymer of not grafting, the polymer that connects branch and the homopolymers of grafted monomers or the copolymer three part quality of grafting mix monomer).Percent grafting is a parameter of expression grafting efficiency.Available percent grafting %=(by the monomer mass/total polymer mass of grafting) * 100 expression.The larger active group that can participate in reacting of percent grafting is more, is conducive to improve the tack of graft copolymer and metal.The too high resin that also can make of percent grafting has to a certain degree degraded on the other hand, thereby the mechanical property of resin itself is descended to some extent, and material cost also can correspondingly improve simultaneously.Generally speaking, if percent grafting is too high, can with accordingly not graft resin carry out blend dilution, make it performance and improve, reduce simultaneously cost.
According to composite metal plate provided by the invention, in order to increase the adhesive force of resin bed and metal, described resin bed is preferably the resin bed of the polyolefin blend of other resin and maleic anhydride graft, the weight ratio of the polyolefin blend of described other resin and described maleic anhydride graft is preferably (0.5-10): 1, more preferably (1-8): 1, most preferably be (1.5-6): 1.
According to composite metal plate provided by the invention, the thickness of described resin bed is preferably the 5-100 micron.
According to composite metal plate provided by the invention, described metal base can be various metal bases, for example aluminium, aluminium alloy, steel, copper, copper alloy, tin, nickel or zinc.And preferred aluminium, aluminium alloy or steel.Wherein steel can be various cold-rolled steels, hot rolling steel or stainless steel.Aluminium plate thickness or steel plate thickness are not limit, and decide as required.
According to composite metal plate provided by the invention, when described metal base was aluminium, the chemical surface treatment layer that is attached to described metallic substrate surface was anodic oxide coating, and the thickness of described anodic oxide coating is the 0.2-20 micron, is preferably the 3-6 micron.
According to composite metal plate provided by the invention, when described metal base was steel, the chemical surface treatment layer that is attached to described metallic substrate surface was phosphate layer or chromate coating, and the thickness of described phosphate layer or chromate coating is the 1-50 micron, is preferably the 3-8 micron.
The preparation method of composite metal plate provided by the invention comprises, metal base is carried out chemical surface treatment, wherein, the method also is included in and forms one deck or which floor resin bed on the metal base that chemical surface treatment crosses, described resin bed is the polyolefin resin layer of maleic anhydride graft, perhaps be the resin bed of the polyolefin blend of other resin and maleic anhydride graft, described other resin is Merlon, polycaprolactam, polyolefin, PETG or polybutylene terephthalate (PBT).
According to preparation method provided by the invention, in the preferred case, for the resin bed conforming layer is pressed on the metal base, the thickness of the resin bed that the metal base of crossing in chemical surface treatment forms is the 5-100 micron.Described resin bed can be individual layer or two-layer more than.These resin beds can be the omnidirectional resin moldings that do not stretch, and also can be resin moldings unidirectional or that biaxial tension is directed.
According to preparation method provided by the invention, before chemical surface treatment, carry out respectively to metallic substrate surface the pre-treatment of oil removing, rust cleaning.Method to pre-treatment has no particular limits, and can adopt to well known to a person skilled in the art various deoiling methods, as long as can remove the grease that is attached to metallic substrate surface, removes inhomogeneous oxide and gets final product.After for example can adopting the alkalescent degreaser to carry out ungrease treatment, in aqueous solution of nitric acid, carry out afterwards the method that decontamination is processed.Above-mentioned pre-treatment can also be carried out etching to metal base, to substitute the processing of oil removing and rust cleaning, non-staining degree is arrived in the metal base alligatoring, to improve chemical surface treatment layer fixing in metallic substrate surface.At this, the method for etching method can be enumerated the alkaline etching that uses NaOH for well known to a person skilled in the art the whole bag of tricks, uses the acid etching of sulfuric acid, hydrofluoric acid, and the etching of in the acid solution of nitric acid, being undertaken by electrolysis etc.
According to preparation method provided by the invention, when described metal base was aluminium, the chemical treatment of carrying out on the aluminium surface was anodic oxidation, form thick for the 0.2-20 micron, be preferably the anodic oxide coating of 3-6 micron.
Anodised method is conventionally known to one of skill in the art, carry out anodised electrolyte aqueous solution can adopt various for anodised electrolyte aqueous solution, for example sulfuric acid, phosphoric acid, chromic acid, oxalic acid, adipate ester, malonate, phthalic acid ester or esters of silicon acis.But from concerning rete dissolubility, oxidation efficiency and loose structure, the electrolyte solution of preferably sulfuric acid, phosphoric acid, chromic acid or oxalic acid.
The electrolytic conditions such as the pH that as known to the skilled person, the thickness of anodic oxide coating can be by the electrolysis time of regulating aluminium sheet, the kind of electrolyte aqueous solution, electrolytical concentration, electrolyte aqueous solution, the temperature of electrolyte aqueous solution, applied voltage, current density are adjusted.The time of electrolysis is different with electrolytic condition, is generally 5-40 minute, is preferably 5-15 minute.
As known to the skilled person, anodised condition is generally, electrolytical concentration is 2-300g/l in the electrolyte aqueous solution, the temperature of electrolyte aqueous solution is 13-26 ℃, take aluminium sheet as anode, as negative electrode, applied voltage is 3-200V with insoluble conductive material, and current density is 0.8-10A/dm
2
According to preparation method provided by the invention, described metal base is steel, described metal base is carried out chemical surface treatment for carrying out phosphatization on the surface of steel and process or chromate is processed, forming thick is 1-50 micron, the phosphate layer that is preferably the 3-8 micron or chromate coating.
To the surface of steel carry out that phosphatization is processed or chromate to process be well known to a person skilled in the art, when carrying out the phosphatization processing on the surface of steel, Phosphating Solution can adopt various known Phosphating Solutions for steel plate being carried out phosphatization, for example zinc system, zinc calcium system, manganese system, MnZn system or iron system.Various Phosphating Solution in the present invention Phosphating Solution is not particularly limited, because all can form main component for the phosphate layer of the crystallization water chemical surface treatment layer as steel plate.
For example parkerized process is generally, and need are carried out parkerized metallic plate, and to put into temperature be 50-70 ℃ Phosphating Solution, carries out phosphatization and processed 20 minutes.Described Phosphating Solution is for well known to a person skilled in the art various Phosphating Solutions, and for example the Phosphating Solution of zinc system is the Zn (H that contains 60g/L
2PO
4)
22H
2Zn (the NO of O, 80g/L
3)
26H
2The Na of O, 1.6g/L
2NO
2H with 9ml/L
3PO
4The aqueous solution.
For example the process of chromate processing is generally, and needs is carried out the metallic plate of chromate processing and puts into the Treatment Solution that temperature is controlled at 60 ℃, infiltrates after 15 minutes, with distilled water clean metal plate.Described Treatment Solution is for well known to a person skilled in the art, for example for containing the aqueous solution of 25% sulfuric acid, 2.5% sodium dichromate.
According to preparation method provided by the invention, the method that resin bed is attached on the metallic plate has no particular limits, can adopt and well known to a person skilled in the art known method, extruders such as available T-shaped mould, I pattern is extruded the resin of heating and melting with film-form, and directly extrudes the extrusion molding of lamination at metallic plate; Also the ready-made resin beds such as available blowing, T modulus method, rolling process are covered on the metallic plate that is heated to melting point resin, clamp the lay-up method that resin bed and metallic plate and lamination cover with a pair of laminating roll.
The below adopts the mode of embodiment that the present invention is described in further detail.
Embodiment 1
Metal base is selected the thick aluminium sheet of 0.3mm (JIS1100) that is
1, the pre-treatment of aluminium sheet
Under 50 ℃ temperature, aluminium sheet is immersed in 10% sodium hydrate aqueous solution, to 30 seconds of surface of aluminum plate etch processes, then, neutralize with 10% aqueous solution of nitric acid, washed for 10 seconds with water.
2, the anodized of aluminium sheet
Then, the immersion of the aluminium sheet after the above-mentioned pre-treatment is contained the 180g/L concentrated sulfuric acid and 0.03g/LAl
2(SO
4)
3Electrolyte in, with voltage and the 8A/dm of 25V
2Current density, to this aluminium sheet anodic oxidation 5 minutes, having formed thick is 4.5 microns porous anode layer.Then wash 30 seconds of aluminium sheet after the anodic oxidation with water, dry under 80 ℃ temperature.
3, preparation composite metal plate
Resin or blending resin and their performance indications of 9 kinds of maleic anhydride grafts have been listed in the table 1.
It is 50 microns molten resin layer that polypropylene (PP-g-MAH) resin of the maleic anhydride graft of sequence number in the table 11 is extruded thickness by the T-shaped die head of extruder, by carrying out the hot pressing lamination on the aluminium sheet after hot-pressing roller resin bed and the above-mentioned processing of melt temperature that is preheating to the PP-g-MAH resin, then carry out chilling by cold drum.Obtain the metal composite panel products.
Table 1
| Sequence number | Plastic type | Melt temperature (℃) | Percent grafting (%) | The blend ratio | Cantilever beam notched Izod impact strength (J/m) |
| 1 | PP-g-MAH | 180 | 1 | Not blend | 116 |
| 2 | PP/PP-g-MAH | 180 | 3 | 4∶1 | 108 |
| 3 | PA6/PP-g-MAH | 230 | 5 | 2∶1 | 101 |
| 4 | POE-g-MAH | 160 | 1.5 | Not blend | Elastomer |
| 5 | PA6/POE-g-MAH | 275 | 6 | 2∶1 | 122 |
| 6 | PC/ABS-g-MAH | 285 | 10 | 9∶1 | 580 |
| 7 | PET/PP-g-MAH | 280 | 7 | 4∶1 | 107 |
| 8 | PE-g-MAH | 190 | 1.3 | Not blend | 172 |
| 9 | LDPE/PE-g-MAH | 185 | 0.1 | 0.5∶1 | 153 |
Embodiment 2
Prepare the metal composite aluminium sheet according to the method for describing among the embodiment 1, different is, the aluminium sheet after the pre-treatment was carried out anodic oxidation 5 minutes, and obtaining thick is 20 microns anodic oxide coating; And the resin extruded thickness of polypropylene (PP-g-MAH) of the polypropylene that adopts sequence number 2 in the table 1 and polyacrylic blending resin (PP/PP-g-MAH) the replacement maleic anhydride graft of maleic anhydride graft is 5 microns molten resin layer.Finally obtain the metal composite panel products.
Embodiment 3
Prepare the metal composite aluminium sheet according to the method for describing among the embodiment 1, different is, the aluminium sheet after the pre-treatment was carried out anodic oxidation 5 minutes, and obtaining thick is 0.2 micron anodic oxide coating; And the resin extruded thickness of polypropylene (PP-g-MAH) of the polypropylene that adopts sequence number 3 in the table 1 and polyacrylic blending resin (PP/PP-g-MAH) the replacement maleic anhydride graft of maleic anhydride graft is 100 microns molten resin layer.Finally obtain the metal composite panel products.
Embodiment 4-9
Prepare the metal composite aluminium sheet according to the method for describing among the embodiment 1, different is, adopts respectively sequence number 4-9 resin in the table 1 to replace polypropylene (PP-g-MAH) resin of maleic anhydride graft, finally obtains the metal composite panel products.
Embodiment 10
It is the steel plate (SUS304) of 0.3mm that metal base is selected thickness
1, the pre-treatment of steel plate
Clean, after the drying, with chloroform degreasing 10 minutes, then under 50 ℃ temperature, with 30 seconds of 10% sodium hydrate aqueous solution immersion steel plate, then carry out neutralisation treatment with 10% aqueous solution of nitric acid with MEK, washed for 10 seconds with water, drying.
2, the phosphatization of steel plate is processed
It is in 25 ℃ the low-temperature zinc-based phosphatization liquid that contains 35g/L Mazhev salt (two hypophosphite monohydrate dihydro manganese), 150g/L zinc nitrate, 6g/L zinc oxide and 4g/L sodium fluoride that steel plate after the above-mentioned pre-treatment is immersed temperature, phosphatization was processed 30 minutes, then dry under 80 ℃ temperature, obtaining thick at surface of steel plate is 0.5 micron phosphate layer.
3, preparation composite metal plate
It is 50 microns molten resin layer that polypropylene (PP-g-MAH) resin of the maleic anhydride graft of sequence number in the table 11 is extruded thickness by the T-shaped die head of extruder, make on the steel plate after resin bed and the above-mentioned processing that is preheating to corresponding resin melting temperature by hot-pressing roller and to carry out the hot pressing lamination, then carry out chilling by cold drum.Obtain the metal composite panel products.
Embodiment 11
1, the pre-treatment of steel plate
Carry out pre-treatment according to the method that embodiment 10 describes.
2, the chromate of steel plate is processed
To be 60 ℃ the chromatedsolution (concentrated sulfuric acid (98% in temperature through the steel plate of above-mentioned pre-treatment, 5 weight portions), sodium dichromate (2.5 weight portion), water (72.5 weight portion)) infiltrate 10 minutes in, then clean half a minute with distilled water, last oven dry 2 minutes in 70 ℃ baking oven, obtaining thick at surface of steel plate is 1 micron chromate coating.
3, preparation composite metal plate
It is 5 microns molten resin layer that polypropylene (PP-g-MAH) resin that the polyacrylic blending resin (PP/PP-g-MAH) of the polypropylene of sequence number in the table 12 and maleic anhydride graft is replaced maleic anhydride graft is extruded thickness by the T-shaped die head of extruder, make on the steel plate after resin bed and the above-mentioned processing that is preheating to corresponding resin melting temperature by hot-pressing roller and to carry out the hot pressing lamination, then carry out chilling by cold drum.Obtain the metal composite panel products.
Embodiment 12
Prepare metal composite steel plate according to the method for describing among the embodiment 10, different is, the steel plate after the pre-treatment is carried out phosphatization processed 10 minutes, and obtaining thick is 50 microns phosphate layer; And the resin extruded thickness of polypropylene (PP-g-MAH) of the polypropylene that adopts sequence number 3 in the table 1 and polyacrylic blending resin (PP/PP-g-MAH) the replacement maleic anhydride graft of maleic anhydride graft is 100 microns molten resin layer.Finally obtain the metal composite panel products.
Embodiment 13-18
Prepare metal composite steel plate according to the method for describing among the embodiment 10, different is, adopts respectively sequence number 4-9 resin in the table 1 to replace polypropylene (PP-g-MAH) resin of maleic anhydride graft, finally obtains the metal composite panel products.
Comparative example 1-5
Metal base is selected the thick aluminium sheet of 0.3mm (JIS1100) that is
5 kinds have been listed in the table 2 without the resin of maleic anhydride graft and their performance indications.
According to the method for describing in the step 1 and 2 among the embodiment 1 above-mentioned aluminium sheet is carried out respectively pre-treatment and anodized.Then, respectively 5 kinds of resins in the table 2 being extruded thickness by the T-shaped die head of extruder is 50 microns molten resin layer, make on the aluminium sheet after this resin bed and the above-mentioned processing that is preheating to corresponding resin melting temperature by hot-pressing roller and to carry out the hot pressing lamination, then carry out chilling by cold drum.Respectively obtain the composite metal plate product.
Table 2
| Sequence | Plastic type | Melt temperature (℃) | Cantilever beam notched Izod impact strength (J/m) |
| 10 | PP | 190 | 101 |
| 11 | PA6 | 235 | 98 |
| 12 | PC | 290 | 860 |
| 13 | PET | 285 | 110 |
| 14 | LDPE | 185 | 146 |
Comparative example 6
Metal base is selected the thick aluminium sheet of 0.3mm (JIS1100) that is
According to the method for describing in the step 1 and 2 among the embodiment 1 above-mentioned aluminium sheet is carried out respectively pre-treatment and anodized.Then, on the aluminium sheet after the above-mentioned processing with 50mg/m
2Coating amino-organosilanes coupling agent, to be dried after, this aluminium sheet is heated to 250 ℃ heat-treats.Then the 5th kind of resin PA6/POE-g-MAH in the table 1 being extruded thickness by the T-shaped die head of extruder is 50 microns molten resin layer, make on the aluminium sheet after resin bed and the above-mentioned processing of melt temperature that is preheating to PA6/POE-g-MAH by hot-pressing roller and to carry out the hot pressing lamination, then carry out chilling by cold drum.Respectively obtain the composite metal plate product.
Comparative example 7
Metal base is selected the thick aluminium sheet of 0.3mm (JIS1100) that is
According to the method for describing in the step 1 and 2 among the embodiment 1 above-mentioned aluminium sheet is carried out respectively pre-treatment and anodized.Then, on the aluminium sheet after the above-mentioned processing with roll coater coating be dissolved in butanone bisphenol A type epoxy resin (molecular weight: 380, epoxide equivalent: 180-200), place 6 hours dryings under the normal temperature, forming thickness is filming of 1 μ m.At 350 ℃ this is filmed and to heat-treat.Then the 5th kind of resin PA6/POE-g-MAH in the table 1 being extruded thickness by the T-shaped die head of extruder is 50 microns molten resin layer, make on the aluminium sheet after this resin bed and the above-mentioned processing of melt temperature that is preheating to PA6/POE-g-MAH by hot-pressing roller and to carry out the hot pressing lamination, then carry out chilling by cold drum.Respectively obtain the composite metal plate product.
Performance evaluation
1, the processing tack of resin bed
It is 50 millimeters that composite metal plate is struck out diameter, highly is 30 millimeters circular cylindrical shell, makes resin bed be positioned at the inboard of circular cylindrical shell.
Cut out the crossed grid spirte with drawing the lattice device at above-mentioned circular cylindrical shell medial surface, otch is deep to and exposes metal base; Respectively brush five times with the hairbrush diagonal, pull open again on otch with tape sticker; Observe the situation of grid area, available magnifying glass is observed; Divide the quality of adhesive force according to following standard class:
Good: the edge of otch is fully smooth, and the grid edge is without any peeling off;
Better: have small pieces to peel off in the intersection of otch, actual spoilage is no more than 5% in stroke lattice district;
Relatively poor: have small pieces to peel off in the intersection of otch, actual spoilage surpasses 5% in stroke lattice district, but less than 10%;
Poor: the edge of otch and/or intersection have is peeled off, and its area is greater than 10%.
2, the shock-resistant processability of resin bed
At the wide sample that is 30 millimeters of next block length of bottom of cylinder center cutting of above-mentioned circular cylindrical shell, from the metallic plate side of 1 meter height ball falling impact sample.Sample be attached with resin bed one side since ball falling impact cause the prominence place and to be soaked with the sponge that concentration is 1% NaCl solution, this sample is applied 6 volts voltage, measure the electric current that passes through.Current value is lower, shows that the crackle of resin bed generation is less, and its resistance to impact is better.Standard of evaluation is as follows:
Good: less than 0.05mA
Better: more than the 0.05mA, and less than 0.1mA
Relatively poor: more than the 0.1mA, and less than 0.3mA
Poor: more than the 0.3mA.
3, with the tack of casting resin
The circular cylindrical shell of above-mentioned gained is put into the injection machine mould of size and circular cylindrical shell coupling, is 200 ℃ with mould and die preheating to temperature, and polycarbonate resin is injected the inboard that circular cylindrical shell is attached with resin bed.
With above injection moulding sample fall 2 meters eminences, each sample test is done 50 times; Then, observe metallic plate and whether peel off with the Merlon of injection moulding, available magnifying glass observation, do not peel off for well; What slightly peel off is relatively poor; What obviously peel off is poor.
4, the apparent property of resin after the punch process
The wide sample that is 30mm of next block length of bottom of cylinder center cutting at above-mentioned circular cylindrical shell, from the height falling sphere of 1m, metal one side of impact specimen, the prominence that is covered with resin bed one side at sample observes with magnifying glass whether the phenomenon of turning white is arranged, if without turning white phenomenon, then apparent property is good; If just slightly turn white, then be better; Large stretch of blushing is arranged, and then apparent property is poor.
5, high/low-temperature impact performance test
Above-mentioned circular cylindrical shell is put into low temperature impact test box (the rich fine jade equipment in Shanghai Co., Ltd, GDWJ50) in, between two temperature of-40 ℃ and 85 ℃, change, each temperature kept 2 hours, totally 5 cycles, continued 20 hour less than 3 minutes conversion time, observe sample, do not occur that resin bed and metallic plate are peeled off or circular cylindrical shell does not deform into good; If it is that slight deformation is then for relatively poor that resin bed and metallic plate are peeled off circular cylindrical shell; If resin bed and metallic plate are peeled off or the circular cylindrical shell distortion then is poor.
Above-described " good " is expressed as " zero ";
" better " is expressed as " ⊙ ";
" relatively poor " be expressed as "
";
" poor " is expressed as " * ".
To embodiment 1-18, the resulting composite metal plate of comparative example 1-7 is estimated by above-mentioned method of evaluating performance, and acquired results is listed in the table 3.
Can find out that from the evaluation result of table 3 resin bed processing tack and the shock-resistant processability of resin bed of clad metal sheet provided by the present invention are all fine, and apparent property is also all fine after high/low-temperature impact performance and the resin bed processing.And, to compare as the processing film layer of metallic plate with adopting without the standby clad metal sheet of the resin of maleic anhydride graft, the bisphenol A type epoxy resin that adopts the amino-organosilanes coupling agent or be dissolved in butanone, above-mentioned performance is all good a lot.
Table 3
| Resin bed processing tack | The shock-resistant processability of resin bed | The high/low-temperature impact performance | Apparent property after the resin bed processing | |
| Embodiment 1 | ○ | ○ | ○ | ○ |
| Embodiment 2 | ○ | ○ | ○ | ○ |
| Embodiment 3 | ○ | ○ | ○ | ⊙ |
| Embodiment 4 | ○ | ○ | ○ | ○ |
| Embodiment 5 | ○ | ⊙ | ○ | ○ |
| Embodiment 6 | ○ | ○ | ○ | ○ |
| Embodiment 7 | ○ | ○ | ○ | ○ |
| Embodiment 8 | ○ | ○ | ○ | ○ |
| Embodiment 9 | ○ | ○ | ○ | ○ |
| Embodiment 10 | ○ | ⊙ | ○ | ○ |
| Embodiment 11 | ○ | ○ | ○ | ○ |
| Embodiment 12 | ○ | ○ | ○ | ○ |
| Embodiment 13 | ○ | ○ | ○ | ○ |
| Embodiment 14 | ○ | ○ | ○ | ○ |
| Embodiment 15 | ○ | ○ | ○ | ○ |
| Embodiment 16 | ○ | ○ | ○ | ○ |
| Embodiment 17 | ○ | ○ | ○ | ⊙ |
| Embodiment 18 | ○ | ○ | ○ | ○ |
| Comparative example 1 | × | × | × | ⊙ |
| Comparative example 2 | × | × | × | × |
| Comparative example 3 | × | × | × | ○ |
| Comparative example 4 |
 |
× |
 |
× |
| Comparative example 5 | × | × | × | ○ |
| Comparative example 6 |
 |
 |
○ | × |
| Comparative example 7 |
 |
 |
○ | × |
Claims (14)
1. composite metal plate, chemical surface treatment layer and one deck or which floor resin bed that this composite metal plate comprises metal base and is attached to successively this metallic substrate surface, it is characterized in that, described resin bed is the resin bed of the polyolefin blend of other resin and maleic anhydride graft, described other resin is Merlon, polycaprolactam, polyolefin, PETG or polybutylene terephthalate (PBT), and the weight ratio of the polyolefin blend of described other resin and maleic anhydride graft is (0.5-10): 1.
2. composite metal plate according to claim 1, wherein, the cantilever beam notched Izod impact strength of the resin of described resin bed is 100-650J/m, in the vistanex of described maleic anhydride graft, the percent grafting of maleic anhydride is 0.1-15%.
3. composite metal plate according to claim 1, wherein, described polyolefin is polypropylene, polyethylene, polystyrene, SB, ethene-1-octene copolymer, EPM, ethylene propylene diene rubber or acrylonitrile-butadiene-styrene copolymer.
4. composite metal plate according to claim 1, wherein, the thickness of described resin bed is the 5-100 micron.
5. composite metal plate according to claim 1, wherein, described metal base is aluminium, aluminium alloy, steel, copper, copper alloy, tin, nickel or zinc.
6. composite metal plate according to claim 1 or 5, wherein, described metal base is aluminium, and the chemical surface treatment layer that is attached to described metallic substrate surface is anodic oxide coating, and the thickness of described anodic oxide coating is the 0.2-20 micron.
7. composite metal plate according to claim 1 or 5, wherein, described metal base is steel, and the chemical surface treatment layer that is attached to described metallic substrate surface is phosphate layer or chromate coating, and the thickness of described phosphate layer or chromate coating is the 1-50 micron.
8. the preparation method of composite metal plate claimed in claim 1, the method comprises carries out chemical surface treatment with metal base, it is characterized in that, the method also is included in and forms one deck or which floor resin bed on the metal base that chemical surface treatment crosses, described resin bed is the resin bed of the polyolefin blend of other resins and maleic anhydride graft, described other resin is Merlon, polycaprolactam, polyolefin, PETG or polybutylene terephthalate (PBT), the weight ratio of the polyolefin blend of described other resin and maleic anhydride graft is (0.5-10): 1.
9. preparation method according to claim 8, wherein, the cantilever beam notched Izod impact strength of the resin of the resin bed of described formation is 100-650J/m, in the vistanex of described maleic anhydride graft, the percent grafting of maleic anhydride is 0.1-15%.
10. preparation method according to claim 8, wherein, described polyolefin is polypropylene, polyethylene, polystyrene, SB, ethene-1-octene copolymer, EPM, ethylene propylene diene rubber or acrylonitrile-butadiene-styrene copolymer.
11. preparation method according to claim 8, wherein, the thickness that the metal base of crossing in chemical surface treatment forms resin bed is the 5-100 micron.
12. preparation method according to claim 8, wherein, described metal base is aluminium, aluminium alloy, steel, copper, copper alloy, tin, nickel or zinc.
13. according to claim 8 or 12 described preparation methods, wherein, described metal base is aluminium, and the described chemical surface treatment that metal base is carried out is for to carry out anodic oxidation on the surface of aluminium, and forming thick is the anodic oxide coating of 0.2-20 micron.
14. according to claim 8 or 12 described preparation methods, wherein, described metal base is steel, described metal base is carried out chemical surface treatment for carrying out phosphatization on the surface of steel and process or chromate is processed, and forming thick is phosphate layer or the chromate coating of 1-50 micron.
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