CN101754666A - Conductive precoating aluminum alloy plate - Google Patents
Conductive precoating aluminum alloy plate Download PDFInfo
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- CN101754666A CN101754666A CN200810184623A CN200810184623A CN101754666A CN 101754666 A CN101754666 A CN 101754666A CN 200810184623 A CN200810184623 A CN 200810184623A CN 200810184623 A CN200810184623 A CN 200810184623A CN 101754666 A CN101754666 A CN 101754666A
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Abstract
The invention provides and a kind ofly have good conductivity, and the good conductive precoating aluminum alloy plate of anti-finger printing.It comprises: the conductive layer 4 that forms on the chemical composition coating 3 that forms on face of the substrate 2 that aluminium alloy plate constitutes, this substrate 2 or the two sides and this chemical composition coating 3.This conductive layer 4 comprises the synthetic resin more than a kind or 2 kinds that is selected from polyurethane resin, ionic polymer resin, polyvinyl resin, epoxy resin, fluororesin, the mylar.The thickness T of conductive layer 4 is 0.05 μ m～1.0 μ m, and the surface roughness Ra of substrate 2 is 0.1 μ m～0.8 μ m, and the thickness T of conductive layer 4 is 0.07～4.0 with the ratio (T/Ra) of the surface roughness Ra of substrate 2.Conductive layer 4 preferably also contains the cataloid that primary particle diameter is 5nm～80nm.
Description
Technical field
The present invention relates to the high conductive precoating aluminum alloy plate that electric apparatus housing for example etc. uses.
Background technology
All the time, the surface of aluminium alloy plate has the good characteristic that needn't implement to cover with paint, lacquer, colour wash, etc. after excellent corrosion resistance, light weight and the moulding with the precoating aluminum alloy plate that the synthetic resin coating coating forms.Therefore, the pre-coating aluminium alloy plate is widely used as the material of electronic instrument housings such as tame electrical article and OA instrument etc.
On the other hand, under most occasions, these electronic instruments generate electromagnetic waves, and the parts as uses such as housings in order to suppress electromagnetic harmful effect, are necessary for electroconductive component.General resin is when being overlayed on aluminium alloy plate when surface, then produces chargedly, causes various electronic failures.Therefore, make above-mentioned synthetic resin coating (organic resin class coating) have conductivity.
Therefore, the following various metallic finishes plates that make it have conductivity are proposed before this.
Patent documentation 1 and patent documentation 2 disclose a kind of composite coated aluminium sheet that contains the organic membrane of conductive materials such as iron phosphide, graphite, carbon black with the regulation ratio that is formed with.
Patent documentation 4 shows and is formed with the aluminium alloy plate that contains the organic resin layer of carbon black with the regulation ratio.
Patent documentation 5, patent documentation 6, patent documentation 7, patent documentation 8 propose to contain sheet, flakey or spherical Ni filler in filming.
The aluminium sheet that contains the Ni particulate during patent documentation 9, patent documentation 10, patent documentation 11 propose to make and film.
Patent documentation 12 propositions contain the aluminium sheet of the resin molding of Zr.
But, in recent years, in high precision int that carries out computer and enhancement of environment, need to suppress the harmful effect that produces by electromagnetic wave more.But, electroconductive resin before this, the conduction probability that is produced because of the contact of conductance and electrode can not adapt therewith.
[patent documentation 1] spy opens flat 5-309331 communique
[patent documentation 2] spy opens flat 5-311454 communique
[patent documentation 3] spy opens flat 7-313930 communique
[patent documentation 4] spy opens flat 7-90604 communique
[patent documentation 5] spy opens the 2004-68042 communique
[patent documentation 6] spy opens flat 5-320934 communique
[patent documentation 7] spy opens flat 5-65664 communique
[patent documentation 8] spy opens flat 7-246679 communique
[patent documentation 9] spy opens flat 7-211131 communique
[patent documentation 10] spy opens flat 7-314601 communique
[patent documentation 11] spy opens flat 8-267656 communique
[patent documentation 12] spy opens the 2001-205730 communique
Summary of the invention
Therefore, in above-mentioned any prior art, in organic resin, must contain various as mentioned above in a large number conductive materials.On the other hand, these conductive materials become the impurity that this film performance is reduced in organic resin.That is, reduce by the ratio that has a large amount of impurity in filming, make the organic resin of bearing the adhesive effect, the tack and the mouldability of filming reduce greatly.
In addition, about conductivity, because there is the unstable such problem of this value in the distribution bias of conductive material.
As mentioned above, even need conductive material conduction itself and the also maintained ultrafine particle of thickness as thin as a wafer.In addition, resin molding itself also must be made the trickle film that reaches very thin films character uniformly.
In addition, conductive precoating aluminum alloy plate, for example, most as materials such as housings.Yet housing etc. are because the chance of contact human eye is many, so must suppress the outward appearance deterioration that causes such as to adhere to by fingerprint.
The present invention proposes in view of above-mentioned existing problem points, and a kind of good conductivity that has is provided, and the good conductive precoating aluminum alloy plate of anti-finger printing.
Conductive precoating aluminum alloy plate of the present invention is characterized in that, it comprises: the conductive layer that forms on the chemical composition coating that forms on the substrate that aluminium alloy plate constitutes and face of this substrate or the two sides and this chemical composition coating.
This conductive layer comprises the synthetic resin more than a kind or 2 kinds that is selected from polyurethane resin, ionic polymer resin, polyvinyl resin, epoxy resin, fluororesin, the mylar.
The thickness T of above-mentioned conductive layer is 0.05 μ m～1.0 μ m.
The surface roughness Ra of aforesaid substrate is 0.1 μ m～0.8 μ m.
The thickness T of above-mentioned conductive layer is 0.07～4.0 with the ratio (T/Ra) of the surface roughness Ra of aforesaid substrate.
In the present invention, conductive layer is extremely thin as mentioned above, and its thickness is 0.05 μ m～1.0 μ m.And this conductive layer does not have the structure of original such a large amount of dispersed electro-conductive materials, and above-mentioned conductive layer itself has conductivity.Therefore, can both suppress coating adhesion and reduce the conductivity of getting back.In addition, because above-mentioned filming itself have conductivity, so can almost there be very good conductivity such as conductance deviation.
In addition, above-mentioned conductive layer is made by the above-mentioned specific synthetic resin of enumerating, because the hydrophobicity of these synthetic resin is stronger, forms conductive layer by adopting these synthetic resin, can obtain being difficult to produce the anti-finger printing of fingerprint.
Also have, the mechanism of above-mentioned conductive layer performance good electric conductivity is also not fully aware of.Yet, at least to having the substrate of 0.1 μ m～0.8 μ m surface roughness Ra as mentioned above, adopt above-mentioned specific synthetic resin, forming thickness T is the conductive layer of 0.05 μ m～1.0 μ m, and the thickness T that active adoption makes above-mentioned conductive layer and the ratio (T/Ra) of the surface roughness Ra of aforesaid substrate are 0.07～4.0 structure, support as following embodiment, can obtain good conductivity and anti-finger printing.
Thus, can obtain having good conductivity and the good conductive precoating aluminum alloy plate of anti-finger printing.
Description of drawings
Fig. 1 is the key diagram of the structure of conductive precoating aluminum alloy plate among the expression embodiment.
Fig. 2 is the key diagram of the evaluation method of punch process among the expression embodiment.
Fig. 3 is the key diagram of the Bowden test method(s) of marresistance evaluation method among the expression embodiment.
The explanation of symbol
1 conductive precoating aluminum alloy plate
2 substrates
3 chemical composition coatings
4 conductive layers
Embodiment
Conductive precoating aluminum alloy plate of the present invention, as mentioned above, it comprises: the conductive layer that forms on the chemical composition coating that forms on substrate, face of this substrate or the two sides that aluminium alloy plate constitutes and this chemical composition coating.
As the aluminium alloy that constitutes aforesaid substrate, can adopt various aluminium alloys in the present invention according to purposes.Concrete have 5000 be, 6000 various alloy systems such as be.
In addition, consider that from the reason that makes the high-strength conductive precoating aluminum alloy plate aforesaid substrate preferably contains Mg 1.0～5.0 quality %.
In addition, as the chemical composition coating that forms on the aforesaid substrate, can adopt by chromate such as chromium phosphate hydrochlorate, chromic acid chromium hydrochlorates and handle, utilize processings of filming of chemistry such as non-chromate processing such as titanium phosphate beyond the chromium compound and basic zirconium phosphate, molybdenum phosphate, trbasic zinc phosphate, zirconia, the film that promptly so-called chemical conversion processing obtains.
Because the existence of the base treatment layer that this chemical composition coating constitutes, so the substrate that aluminium alloy plate constitutes and can effectively improve as the tack of the synthetic resin coating film of conductive layer.In addition, owing to present superior corrosion resistance, the bottom corrosion of filming that corrosive substances such as water, chlorine compound cause when the aluminium alloy plate surface impregnation is suppressed, and can seek to prevent to be coated with film rupture and film and peel off.
Also have, in the chemical conversion processing methods such as above-mentioned chromate processing or non-chromate processing, the type that responds and application type, but adopt any method all can among the present invention.
In addition, the thickness T of above-mentioned conductive layer is 0.05 μ m～1.0 μ m.
As the thickness T of above-mentioned conductive layer during greater than 1.0 μ m, the resistance of above-mentioned conductive layer strengthens, and conductivity reduces, and simultaneously, the mouldability of filming such as punching formation property has the possibility of reduction.Also have, the lower limit of above-mentioned thickness T is considered from the reason that keeps corrosion resistance, is made as 0.05 μ m.
In addition, the surface roughness Ra that is positioned at the aforesaid substrate under the above-mentioned chemical composition coating is 0.1 μ m～0.8 μ m.
When the surface roughness Ra of aforesaid substrate was lower than 0.1 μ m, except that the industrial production difficulty, conductivity had the possibility of decline.On the other hand, when surface roughness Ra during greater than 0.8 μ m, above-mentioned conductive layer is failed the substrate coated fracture phenomena of filming and is taken place, corrosion resistance and punch process, and marresistance, anti-finger printings etc. have the possibility of reduction.
In addition, the thickness T of above-mentioned conductive layer is 0.07～4.0 with the ratio (T/Ra) of the surface roughness Ra of aforesaid substrate.
When above-mentioned T/Ra less than 0.07 the time, have corrosion resistance, punch process, the problem that marresistance and anti-finger printing etc. reduce, on the other hand, when above-mentioned T/Ra greater than 4.0 the time, except that the industrial production difficulty, the problem that exists conductivity to reduce.
In addition, as the coating process of the conductive layer that constitutes above-mentioned conductive layer, be not particularly limited, but can adopt known the whole bag of tricks such as rolling method, scraping article rubbing method, dip coated method, spraying process with coating.In addition, be coated with this conductive layer with coating after for solidifying the condition of cure of formed conductive layer, promptly bake condition etc., can select various conditions with the kind of coating etc. according to each conductive layer.
In addition, preferred above-mentioned conductive layer also contains the cataloid that primary particle diameter is 5nm～80nm.
At this moment, can improve the conductivity of above-mentioned conductive precoating aluminum alloy plate more.
Also have, above-mentioned so-called cataloid means electronegative amorphous silica particles and is dispersed in the colloidal particle that forms in the water.The surface of particle existence-SiOH base ,-OH
-Ion forms electric double layer by basic ion, and by repelling each other between particle, cataloid solution becomes stable status.
Each particle of dispersity is called primary particle before being in cohesion, and above-mentioned so-called primary particle diameter means the diameter of this primary particle.And the particle after the cohesion is called secondary, and the diameter of secondary is called secondary particle diameter.
When the primary particle diameter of above-mentioned cataloid during less than 5nm, resistance increases, and conductivity has the possibility of decline.On the other hand, when the primary particle diameter of above-mentioned cataloid during greater than 80nm, chemical composition coating and film between tack have reduction may or anti-finger printing the possibility of decline is arranged.
In addition dry cataloid, obtain specific area with BET method (specific area measuring method), can obtain above-mentioned each diameter from weight and density by seizing back confiscated property.
Even containing on a small quantity, above-mentioned cataloid also can present above-mentioned effect.And, although improve from conductivity, have chemical composition coating with film between the possible reason consideration that reduces of tack, when the dry weight of above-mentioned conductive layer integral body was made as 100 weight portions, the upper content limit of cataloid was 90 weight portions.In addition, even amount equals or exceeds this content, considering from the reason that effect is saturated, is preferred below 60 weight portions, more preferably below 40 weight portions.
In fact,, when the dry weight of above-mentioned conductive layer integral body is made as 100 weight portions, preferably contain more than above-mentioned cataloid 1 weight portion, more preferably contain more than 5 weight portions in order to obtain desirable effect.
When the dry weight of above-mentioned conductive layer integral body is made as 100 weight portions, preferably contains above-mentioned cataloid 1～60 weight portion, more preferably contain 5～40 weight portions.
In addition, when the dry weight of above-mentioned conductive layer integral body was made as 100 weight portions, above-mentioned conductive layer preferably also contained surfactant 0.1～10 weight portion.
At this moment, the conductivity of above-mentioned conductive precoating aluminum alloy plate can be further improved, marresistance can be improved.
In addition, when the content of above-mentioned surfactant was lower than 0.1 weight portion, above-mentioned effect had the possibility that can not fully obtain, on the other hand, when the content of above-mentioned surfactant during greater than 10 weight portions, although conductivity improves, have chemical composition coating with film between the possibility of tack decline.
In addition, as above-mentioned surfactant, can enumerate ether type, ester type, Etheric ester type surfactant etc.
As surfactant, for example, can adopt the fatty acid ester, carboxylate, alkylsulfonate, alkyl sulfate salt, alkylphosphonic, fatty acid alkanol amides of the oxyalkylene addition product of the above alcohol of hydrocarbyl ether, the monobasic of oxyalkylene addition product of the above alcohol of oxyalkylene addition product, the monobasic of the above alcohol of monobasic etc., can therefrom select a kind to use separately, also can adopt the mixture more than 2 kinds with different structure.
Constitute the alcohol of fatty acid ester of oxyalkylene addition product of hydrocarbyl ether, the above alcohol of monobasic of the oxyalkylene addition product of the above alcohol of oxyalkylene addition product, the monobasic of the above alcohol of above-mentioned monobasic, have 1～6 of hydroxyl.
As this alcohol, if monohydric alcohol, can enumerate the alcohol of 8～23 of carbon numbers, have strand or unsaturated bond in the molecule, circulus also can.Can enumerate octanol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecanol, tetradecyl alchohol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, ethyl-phenol, nonyl phenol etc. particularly, both can adopt a kind ofly separately, also can adopt these mixture.
Further, can enumerate neopentyl glycol, trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, pentaerythrite, dipentaerythritol, 2-butyl-2-ethyl-1, ammediol, 2-methyl-2-propyl group-1, ammediol, 2,2-diethyl-1, ammediol etc.
In addition, consider from lubrification, this point of the water property removed, as above-mentioned alcohol, the alcohol of preferred carbon number 12～18 scopes.
The oxyalkylene addition product of fatty acid ester that constitutes the oxyalkylene addition product of the above alcohol of hydrocarbyl ether, the monobasic of oxyalkylene addition product of the above alcohol of oxyalkylene addition product, the monobasic of the above alcohol of above-mentioned monobasic preferably makes by the oxyalkylene of addition polymerization carbon number 2～6, and more preferably the oxyalkylene by addition polymerization carbon number 2～4 makes.
As the oxyalkylene of carbon number 2～6, can enumerate for example oxirane, expoxy propane, 1,2-epoxy butane (α-epoxy butane), 2,3-epoxy butane (beta epoxide butane), 1,2-epoxy-1-methylpropane, 1,2-epoxy heptane etc. particularly.
Also have, the polymeric species of oxyalkylene etc. is not particularly limited, and the homopolymerization of a kind of oxyalkylene, random copolymerization, block copolymerization, random/block copolymerization etc. such as oxyalkylene also can more than 2 kinds.
In addition, when having on the polyalcohol of 2～6 hydroxyls the addition oxyalkylene, both can addition on all hydroxyls, also only addition on a part of hydroxyl.
Also can use the product of part or all alkyl etherificate of terminal hydroxyl of oxyalkylene addition product of fatty acid ester of the oxyalkylene addition product of the above alcohol of hydrocarbyl ether, the monobasic of oxyalkylene addition product of the above alcohol of the oxyalkylene addition product, the monobasic that constitute the above alcohol of above-mentioned monobasic.
Here, so-called alkyl is the alkyl of carbon number 1～24.
As alkyl, for example can enumerate alkyl, alkenyl, cycloalkyl, alkyl-cycloalkyl, aryl, alkaryl and aralkyl etc.
Alkyl as carbon number 1～24, for example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, the amyl group of straight or branched, the hexyl of straight or branched, the heptyl of straight or branched, the octyl group of straight or branched, the nonyl of straight or branched, the decyl of straight or branched, the hendecyl of straight or branched, the dodecyl of straight or branched, the tritriacontyl of straight or branched, the tetradecyl of straight or branched, the pentadecyl of straight or branched, the palmityl of straight or branched, the heptadecyl of straight or branched, the octadecyl of straight or branched, the nonadecyl of straight or branched, 20 bases of straight or branched, the heneicosyl of straight or branched, the docosyl of straight or branched, the tricosyl of straight or branched, the tetracosyl of straight or branched etc.
Alkenyl as carbon number 2～24, for example, can enumerate vinyl, the acrylic of straight or branched, the cyclobutenyl of straight or branched, the pentenyl of straight or branched, the hexenyl of straight or branched, the heptenyl of straight or branched, the octenyl of straight or branched, the nonene base of straight or branched, the decene base of straight or branched, the hendecene base of straight or branched, the laurylene base of straight or branched, the tridecylene base of straight or branched, the tetradecene base of straight or branched, ten pentaene bases of straight or branched, the hexadecylene base of straight or branched, 17 thiazolinyls of straight or branched, the octadecylene base of straight or branched, 19 thiazolinyls of straight or branched, the icosa alkene base of straight or branched, two hendecene bases of straight or branched, the docosene base of straight or branched, the tricosene base of straight or branched, two tetradecene bases of straight or branched etc.
As the cycloalkyl of carbon number 5～7, for example, can enumerate cyclopenta, cyclohexyl and suberyl etc.
Alkyl-cycloalkyl as carbon number 6～11, for example, can enumerate methylcyclopentyl, dimethylcyclopentyl (comprising the entire infrastructure isomers), Methylethyl cyclopenta (comprising the entire infrastructure isomers), diethyl cyclopenta (comprising the entire infrastructure isomers), methylcyclohexyl, Dimethylcyclohexyl (comprising the entire infrastructure isomers), Methylethyl cyclohexyl (comprising the entire infrastructure isomers), diethyl cyclohexyl (comprising the entire infrastructure isomers), the methyl suberyl, dimethyl suberyl (comprising the entire infrastructure isomers), Methylethyl suberyl (comprising the entire infrastructure isomers), and diethyl suberyl (comprising the entire infrastructure isomers) etc.
As the aryl of carbon number 6～10, for example, phenyl, naphthyl etc. are arranged.
As the alkaryl of carbon number 7～18, tolyl (comprising the entire infrastructure isomers) for example, xylyl (comprising the entire infrastructure isomers), ethylphenyl (comprising the entire infrastructure isomers), the propyl group phenyl of straight or branched (comprising the entire infrastructure isomers), the butyl phenyl of straight or branched (comprising the entire infrastructure isomers), the amyl group phenyl of straight or branched (comprising the entire infrastructure isomers), the hexyl phenyl of straight or branched (comprising the entire infrastructure isomers), the heptyl phenyl of straight or branched (comprising the entire infrastructure isomers), the octyl phenyl of straight or branched (comprising the entire infrastructure isomers), the nonyl phenyl of straight or branched (comprising the entire infrastructure isomers), the decyl phenyl of straight or branched (comprising the entire infrastructure isomers), the hendecyl phenyl of straight or branched (comprising the entire infrastructure isomers), and the dodecyl phenyl of straight or branched (comprising the entire infrastructure isomers).
Aralkyl as 7～12 of carbon numbers, for example, can enumerate benzyl, phenethyl, phenylpropyl (comprising the propyl group isomers), phenyl butyl (comprising the butyl isomers), phenylpentyl (comprising the amyl group isomers), phenyl hexyl (comprising the hexyl isomers) etc.
As the fatty acid ester that constitutes the oxyalkylene addition product of alcohol more than the above-mentioned monobasic, the aliphatic acid of its hydrocarbyl ether, can use any of linear saturated fatty acids, a chain saturated fatty acid, straight chain unrighted acid, side chain unrighted acid.If carbon number, the aliphatic acid with C several 7～22 is preferred.Concrete can enumerate, for example, and sad, n-nonanoic acid, capric acid, methyl laurate, myristic acid, palmitic acid, stearic acid, oleic acid, 20 acid etc.
As above-mentioned carboxylate, for example, can enumerate aliphatic monocarboxylic acid salt, polyoxyethylene alkyl ether carboxylate, N-acyl sarcosinates, N-acyl glutamate etc.As the cationic counter ion counterionsl gegenions that form salt, for example, can enumerate metal ion, ammonium ions etc. such as alkali metal (sodium, potassium, lithium etc.) ion, alkaline-earth metal (magnesium, calcium, barium etc.) ion.
As abovementioned alkyl sulfonate; for example, can enumerate dialkyl sulfosuccinates, paraffin sulfonate, alpha-alkene sulfonate, linear alkylbenzene sulfonate (LAS), strand alkylbenzenesulfonate, naphthalene sulfonate-formaldehyde condensation products, alkylnaphthalene sulfonate, N-methyl-N-acyl group taurine etc.As the cationic counter ion counterionsl gegenions that form salt, for example, can enumerate metal ion, ammonium ions etc. such as alkali metal (sodium, potassium, lithium etc.) ion, alkaline-earth metal (magnesium, calcium, barium etc.) ion.
As alkyl sulfate, for example, can enumerate polyoxyethylene alkyl ether sulfate salt, fatty sulfuric acid etc.As the cationic counter ion counterionsl gegenions that form salt, for example, can enumerate metal ion, ammonium ions etc. such as alkali metal (sodium, potassium, lithium etc.) ion, alkaline-earth metal (magnesium, calcium, barium etc.) ion.
As phosphate, for example, can enumerate alkylphosphonic, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate etc.As the cationic counter ion counterionsl gegenions that form salt, for example, can enumerate metal ion, ammonium ions etc. such as alkali metal (sodium, potassium, lithium etc.) ion, alkaline-earth metal (magnesium, calcium, barium etc.) ion.
In addition, when the dry weight of above-mentioned conductive layer integral body was 100 weight portions, above-mentioned conductive layer preferably also contained interior wax (inner wax) 0.05～15 weight portion.
At this moment, because the existence of interior wax, the coefficient of friction on surface reduces, and can seek the raising of marresistance and the raising of mouldability.In addition, can seek the contact angle reduction of oil content or moisture and the raising of anti-finger printing.
The content of wax is when less than 0.05 weight portion in above-mentioned, and the effect that punching formation property improves has the possibility that can not fully obtain.On the other hand, when greater than 15 weight portions, when reeling in the manufacture process when above-mentioned conductive precoating aluminum alloy plate is produced in batches, interior wax oozes out, and productivity ratio has the possibility of decline.
As wax in above-mentioned, for example, can adopt lanolin, Brazil wax, polyethylene etc.
Here, when adopting polyethylene as above-mentioned synthetic resin, then above-mentioned interior wax can not use polyethylene, and preferred use is not poly lanolin, Brazil wax etc.
In addition, when the dry weight of above-mentioned conductive layer integral body was 100 weight portions, above-mentioned conductive layer also preferably contained nano-sized carbon particle 0.01～10 weight portion that primary particle diameter is 5～100nm.
At this moment, can improve the conductivity of above-mentioned conductive precoating aluminum alloy plate more.
When above-mentioned nano-sized carbon particle primary particle diameter during less than 5nm, above-mentioned effect has the possibility that can not fully obtain.On the other hand, when above-mentioned nano-sized carbon particle primary particle diameter during greater than 100nm, the tack of conductive layer has the possibility of decline.
In addition, when the content of above-mentioned nano-sized carbon particle was lower than 0.01 weight portion, above-mentioned effect had the possibility that can not fully obtain.On the other hand, when above-mentioned nano-sized carbon particle content during, the possibility that is difficult to suitability for industrialized production is arranged greater than 10 weight portions.
In addition, above-mentioned conductive precoating aluminum alloy plate, when adopting the needle electrode method to measure the resistance at different surperficial position, above-mentioned conductive layer 20 places, the surperficial position resistance more than 10 places is below 30 Ω, and the mean value of the surperficial position resistance at above-mentioned 20 places is preferred below 10 Ω.
At this moment, use that can be good in the various uses that must have conductivity.
Also have, so-called above-mentioned needle electrode method, be pin pure made of copper with dome shape needle point of φ 0.2mm, be placed on the conductive layer surface, giving pin does not make needle point run through the load of conductive layer, under this state,, measure the method for the resistance conductive layer value of needle point contact portion by switching between the substrate that exposes at demoulding and the pin.
In addition, the surperficial position that above-mentioned 20 places are different means from the inboard of the end 30mm of A4 version sample, homodisperse 20 places.
In the resistance at the surperficial position that above-mentioned 20 places are different,, the possibility of the part of the shielding difference that generates electromagnetic waves is arranged when 10 resistance of sentencing the upper surface position during greater than 30 Ω.
In addition, the resistance mean value at the surperficial position that above-mentioned 20 places are different has the possibility of the part of the shielding difference that generates electromagnetic waves during greater than 10 Ω.
In addition, the surface roughness Ra of above-mentioned conductive layer surface is that 0.05 μ m～0.6 μ m is preferred.
When the surface roughness Ra of above-mentioned conductive layer surface during less than 0.05 μ m, marresistance and anti-finger printing have the possibility of decline, and on the other hand, when greater than 0.6 μ m, the thickness at the top of coarse protuberance has the tendency of attenuation, corrosion resistance that the possibility of deterioration is arranged.
In addition, above-mentioned conductive precoating cloth aluminium alloy plate, it is preferred using on housing with housing or electronic instrument at electric apparatus.
At this moment, owing to have above-mentioned good conductivity, anti-finger printing, so can obtain good electric apparatus with housing or electronic instrument housing.
Also have, with housing or electronic instrument housing, for example can enumerate electronic instrument housings such as computer body, CD-ROM, DVD, PDA as electric apparatus, the cap of storage medium casings such as casing for electric appliances such as TV, FDD, MD, MO grades.
Embodiment
Embodiment 1
Embodiment and the comparative example relevant with conductive precoating cloth aluminium alloy plate of the present invention are described.
In the present embodiment, change the structure of chemical composition coating, conductive layer etc., as the present invention's product, make 21 kinds of conductive precoating cloth aluminium alloy plates (sample E1～sample E21) shown in the table 2 and 10 kinds of conductive precoating cloth aluminium alloy plates (sample C1～sample C10) shown in the table 3 of product as a comparison, carry out various benchmark tests.
Below this is described in detail.
The conductive precoating aluminum alloy plate 1 of sample E1～sample E21, as shown in Figure 1 any, contain: the substrate 2 that aluminium alloy plate constitutes, the chemical composition coating 3 that on 1 face of this substrate 2 or 2, forms, the conductive layer 4 that on this chemical composition coating 3, forms.
Sample C1～sample C10, its basic structure is with sample E1～sample E21.
When making these samples E1～sample E21, sample C1～sample C10, at first,, adopt the 5052-H34 material of thickness of slab 1.0mm as the substrate 2 that aluminium alloy plate constitutes.The surface roughness Ra of this substrate 2 changes in the scope of 0.05～0.9 μ m.
Secondly, this substrate 2 is implemented chemical composition coating handle, form chemical composition coating 3.Table 1 illustrates 4 kinds of chemical conversions that present embodiment adopts and handles (a～d).
A is handled in chemical conversion: adopt the chromium phosphate hydrochlorate to handle, form the response type chromic acid salt film, make the chromium amount become 20mg/m
2Concrete is that employing is carried out the chemical conversion processing to the groove dip coating that sample is immersed in the chemical pretreatment solution, then, carries out drying in about 100 ℃ atmosphere.
B is handled in chemical conversion: adopt zirconium to handle, form response type non-chromate film, make the zirconium amount become 20mg/m
2It is same that a is handled in processing method and above-mentioned chemical conversion.
C is handled in chemical conversion: adopt the application type chromate to handle, form the application type chromate film, make the chromium amount become 20mg/m
2Specifically, after substrate carries out ungrease treatment, be coated with cloth treating agent, then, in about 100 ℃ atmosphere, carry out drying with the scraping article rubbing method.
D is handled in chemical conversion: adopt the application type zirconium to handle, form application type non-chromate film, make the zirconium amount become 20mg/m
2It is same that d is handled in processing method and above-mentioned chemical conversion.
[table 1]
Secondly, on above-mentioned chemical composition coating 3, form conductive layer 4.As the coating process of conductive layer with coating, above-mentioned the whole bag of tricks is arranged, but adopt the scraping article rubbing method to carry out in the present embodiment, then, become in about 230 ℃ atmosphere in the surface temperature that makes substrate and to keep 40 seconds, bake processing it is solidified, form conductive layer with composition shown in table 2 and the table 3 and thickness T.
Above-mentioned conductive layer coating is to contain compositions such as synthetic resin, cataloid, surfactant and interior wax, makes solid constituent become the coating of forming shown in table 2 and the table 3, adopts isopropyl alcohol, ethanol, ethylene glycol mono-n-butyl ether to make as solvent.
In table 2 and table 3, synthetic resin content, content of colloidal silicon dioxide, interior wax content all refer to the weight with respect to weight 100 weight portions of dried conductive layer integral body.
As the synthetic resin that constitutes conductive layer, 8 kinds of resins such as polyurethane resin, ionic polymer resin, polyvinyl resin, epoxy resin, fluororesin, mylar, polyvinyl alcohol, polyacrylic acid have been prepared.
In table 2 and table 3:
A: polyurethane resin
B: ionic polymer resin
C: polyvinyl resin
D: epoxy resin
B: fluororesin
F: mylar
G: polyvinyl alcohol
H: polyacrylic acid.
In addition, as cataloid, 3 kinds of cataloids of primary particle diameter 3nm, 30nm, 85nm have been prepared.
In addition, as surfactant, 2 kinds of ethylene oxide butyl palmitate, sodium sulfonates have been prepared.
In table 2 and table 3:
EO: ethylene oxide butyl palmitate
NS: sodium sulfonate
In addition, as interior wax, prepare 2 kinds of polyethylene, Brazil waxs.
In table 2 and table 3:
PE: polyethylene
CA: Brazil wax
In addition, as as known from Table 2, sample E1～sample E21, conductive layer is made by the synthetic resin more than a kind or 2 kinds that comprises in polyurethane resin, ionic polymer resin, polyvinyl resin, epoxy resin, fluororesin, the mylar, the thickness T of above-mentioned conductive layer is 0.05 μ m～1.0 μ m, the surface roughness Ra of aforesaid substrate is 0.1 μ m～0.8 μ m, and the thickness T of above-mentioned conductive layer is in 0.07～4.0 scope with the ratio (T/Ra) of the surface roughness Ra of aforesaid substrate.
Secondly, in the present embodiment, 31 kinds of samples shown in his-and-hers watches 2, the table 3 (sample E1～sample E21 and sample C1～sample C10) carry out following various evaluation tests etc.The results are shown in table 4, table 5.
＜conductivity 〉
Conductivity adopts the needle electrode method, estimates by being determined at from the resistance value at the surperficial position at inboard homodisperse 20 places of end 30mm of A4 version sample.The needle electrode method, be pin pure made of copper with dome shape needle point of φ 0.2mm, be placed on the conductive layer surface, giving pin does not make needle point run through the load of conductive layer, under this state, by switching between the substrate that exposes at demoulding and the pin, measure the method for the resistance conductive layer value of needle point contact portion.In the present embodiment, making the load of giving needle point without exception is that 10g carries out.Estimate: the occasion more than 3 is qualified, and the occasion below 2 is defective.
(evaluation criterion)
5 points: show that the resistance value of measuring is that the following ratio of 30 Ω is 100% occasion.
4 points: the resistance value of show measuring is that the following ratio of 30 Ω is～occasion less than 100% more than 80%.
3 points: the resistance value of show measuring is that the following ratio of 30 Ω is～occasion less than 80% more than 50%.
2 points: the resistance value of show measuring is that the following ratio of 30 Ω is～occasion less than 50% more than 30%.
1 point: the resistance value of show measuring is that the following ratio of 30 Ω is～occasion less than 30% more than 10%.
0 point: show that the resistance value of measuring is that the following ratio of 30 Ω is the occasion less than 10%.
＜punch process 〉
Punch process to each sample 50, is carried out bending machining respectively as shown in Figure 2 repeatedly, and the conductive layer by bending machining portion is coated with the number of bends that film rupture disappears and estimates.
Estimate point and represent with 5 grades, the occasion that number of bends is 1 time as the occasion of 5 points, number of bends 2 times as the occasion of 4 points, number of bends 3 times as the occasion of 3 points, number of bends 4 times as the occasion of 2 points, number of bends 5 times as 1 point.The evaluation point is that the occasion more than 3 is qualified, and the evaluation point is that the occasion below 2 is defective.
＜corrosion resistance 〉
Corrosion resistance from the conductive layer surface of sample, adopts cutting knife to carry out cross-cut, and according to the salt spraytest of JIS K5400 regulation, making spray time is the outward appearance of 720 hours back observation samples of spraying.
Estimate point and represent with 5 grades, the unconverted occasion of outward appearance be 5 points, as the occasion of heaving less than filming of 0.5mm be 4 points, as more than the 0.5mm～occasion heaved less than filming of 1mm be 3 points, as more than the 1mm～occasion heaved less than filming of 3mm is that the occasion that 2 points, filming more than 3mm are heaved is 1 point.It is qualified estimating the occasion of point more than 3, and it is defective estimating the occasion of point below 2.
＜marresistance 〉
Marresistance is tested by Bowden shown in Figure 3 and to be carried out.That is, the hard sphere 51 that the diameter of usefulness loading 100g is 1/4 inch slides on the conductive layer surface of the sample of placing on the sample stage 59 50, adopts the slip number of times when being coated with film rupture to estimate.
Estimating point represents with 5 grades, the occasion of slip number of times more than 100 times is 5 points, the slip number of times is more than 75 times～and be 4 points less than 100 times occasions, the slip number of times is more than 50 times～and be 3 points less than 75 times occasions, the slip number of times is more than 25 times～and be 2 points less than 50 times occasions, the slip number of times is 1 point less than 25 times occasion.It is qualified estimating the occasion of point more than 3, and it is defective estimating the occasion of point below 2.
＜anti-finger printing 〉
Anti-finger printing is cut into the area of 50mm * 50mm to each sample, is coated with 10mg/dm at it on the area of half
2The vaseline of amount floods whole sample on 1 post-tensioning, then the revolution mark of perusal vaseline in ethanol.
Estimate point and represent that with 5 grades the occasion of noresidue is 5 points, 1/4 residual occasion is 4 points, and 1/2 residual occasion is 3 points, and 3/4 residual occasion is 2 points, and residual occasion is 1 point comprehensively.It is qualified estimating the occasion of point more than 3, and it is defective estimating the occasion of point below 2.
＜solvent resistance 〉
Solvent resistance, 5 layers of useless cloth of lining soak into trichloroethylene on 1 pound of iron hammer, and it is long to be placed on the 50mm that slides repeatedly on the conductive layer surface of each sample, observes the dissolving of which time film coated surface, variable color.
Estimate point and represent that with 5 grades the occasion more than 10 times is 5 points, more than 7 times～be 4 points less than 10 times occasions, more than 5 times the occasion～be 3 points less than 7 times occasions, more than 2 times～and be 2 points less than 5 times occasions, 1 time occasion is 1 point.It is qualified estimating the occasion of point more than 3, and it is defective estimating the occasion of point below 2.
＜overall merit 〉
Overall merit, the occasion that all items of above-mentioned conductivity, punch process, corrosion resistance, marresistance, anti-finger printing, solvent resistance is all qualified is qualified (being evaluated as zero), and any one underproof occasion of above-mentioned conductivity, punch process, corrosion resistance, marresistance, anti-finger printing, solvent resistance is defective (being evaluated as *).
Table 4
Table 5
As known from Table 4, as the sample E1～E21 of the present invention's product, all assessment item shows excellent characteristic.
Therefore as can be known,, can obtain having good conductivity according to the present invention, and the good conductive precoating aluminum alloy plate of anti-finger printing.
In addition, as known from Table 5, the sample C1 of product, sample C3 as a comparison, because conductive layer is made by polyvinyl alcohol, anti-finger printing is defective.
In addition, the sample C2 of product, sample C4 are made by polyacrylic acid owing to conductive layer as a comparison, and anti-finger printing is defective.
In addition, the sample C5 of product because the thickness T of conductive layer is lower than lower limit of the present invention, can not get corrosion resistance, punch process, marresistance, anti-finger printing etc. and solvent resistance, for defective as a comparison.
In addition, the sample C6 of product as a comparison, because the thickness T of conductive layer surpasses the upper limit of the present invention, the resistance of conductive layer strengthens, and can not get conductance, for defective.
In addition, the sample C7 of product because the surface roughness Ra of substrate is lower than lower limit of the present invention, can not get conductivity, for defective as a comparison.
In addition, above-mentioned conductive layer because the surface roughness Ra of substrate surpasses the upper limit of the present invention, takes place and fails the substrate coated fracture phenomena of filming in the sample C8 of product as a comparison, can not get corrosion resistance, punch process, marresistance, anti-finger printing etc. and solvent resistance, for defective.
In addition, the sample C9 of product owing to (T/Ra) be lower than lower limit of the present invention, can not get corrosion resistance, punch process, marresistance, anti-finger printing and solvent resistance, for defective as a comparison.
In addition, the sample C10 of product owing to (T/Ra) surpass the upper limit of the present invention, can not get conductivity, for defective as a comparison.
Claims (9)
1. conductive precoating aluminum alloy plate is characterized in that, it comprises: the conductive layer that forms on the chemical composition coating that forms on substrate, face of this substrate or the two sides that aluminium alloy plate constitutes and this chemical composition coating; This conductive layer comprises the synthetic resin more than a kind or 2 kinds that is selected from polyurethane resin, ionic polymer resin, polyvinyl resin, epoxy resin, fluororesin, the mylar; The thickness T of above-mentioned conductive layer is 0.05 μ m～1.0 μ m; The surface roughness Ra of aforesaid substrate is 0.1 μ m～0.8 μ m; The thickness T of above-mentioned conductive layer is 0.07～4.0 with the ratio (T/Ra) of the surface roughness Ra of aforesaid substrate.
2. according to the conductive precoating aluminum alloy plate described in the claim 1, it is characterized in that above-mentioned conductive layer also contains the cataloid that primary particle diameter is 5nm～80nm.
3. according to the conductive precoating aluminum alloy plate described in claim 1 or 2, it is characterized in that when the dry weight of above-mentioned conductive layer integral body was 100 weight portions, above-mentioned conductive layer also contained surfactant 0.1～10 weight portion.
4. according to each described conductive precoating aluminum alloy plate in the claim 1～3, it is characterized in that when the dry weight of above-mentioned conductive layer integral body was 100 weight portions, above-mentioned conductive layer also contained interior wax 0.05～15 weight portion.
5. according to each described conductive precoating aluminum alloy plate in the claim 1～4, when the dry weight of above-mentioned conductive layer integral body was 100 weight portions, above-mentioned conductive layer also contained nano-sized carbon particle 0.01～10 weight portion that primary particle diameter is 5～100nm.
6. according to each described conductive precoating aluminum alloy plate in the claim 1～5, it is characterized in that, when adopting the needle electrode method to measure the resistance at different surperficial position, above-mentioned conductive layer 20 places, the resistance at the surperficial position that 10 places are above is below 30 Ω, and the mean value of the resistance at position, surface, above-mentioned 20 places is below 10 Ω.
7. according to each described conductive precoating aluminum alloy plate in the claim 1～6, it is characterized in that the surface roughness Ra of above-mentioned conductive layer surface is 0.05 μ m～0.6 μ m.
8. according to each described conductive precoating aluminum alloy plate in the claim 1～7, it is characterized in that aforesaid substrate contains Mg 1.0～5.0 weight %.
9. according to each described conductive precoating aluminum alloy plate in the claim 1～8, it is characterized in that above-mentioned conductive precoating aluminum alloy plate is used for electric apparatus with housing or electronic instrument housing.
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| CN200810184623A CN101754666A (en) | 2008-12-11 | 2008-12-11 | Conductive precoating aluminum alloy plate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102991018A (en) * | 2011-09-07 | 2013-03-27 | 住友轻金属工业株式会社 | Conductive precoated aluminum alloy board |
| US20130221816A1 (en) * | 2012-02-24 | 2013-08-29 | Htc Corporation | Casing of electronic device and method of manufacturing the same |
| CN103764389A (en) * | 2011-08-31 | 2014-04-30 | 株式会社Uacj | Aluminium coated sheet material for moulding |
| CN105632686A (en) * | 2014-11-05 | 2016-06-01 | 武陟县电业总公司 | Fabrication method for shielding shell of transformer |
| CN113529063A (en) * | 2020-04-20 | 2021-10-22 | 深圳市海运通电子科技有限公司 | High-temperature-resistant coating aluminum shell treatment method |
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2008
- 2008-12-11 CN CN200810184623A patent/CN101754666A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764389A (en) * | 2011-08-31 | 2014-04-30 | 株式会社Uacj | Aluminium coated sheet material for moulding |
| CN103764389B (en) * | 2011-08-31 | 2015-07-01 | 株式会社Uacj | Aluminium coated sheet material for moulding |
| CN102991018A (en) * | 2011-09-07 | 2013-03-27 | 住友轻金属工业株式会社 | Conductive precoated aluminum alloy board |
| CN102991018B (en) * | 2011-09-07 | 2015-05-20 | 住友轻金属工业株式会社 | Conductive precoated aluminum alloy board |
| US20130221816A1 (en) * | 2012-02-24 | 2013-08-29 | Htc Corporation | Casing of electronic device and method of manufacturing the same |
| CN105632686A (en) * | 2014-11-05 | 2016-06-01 | 武陟县电业总公司 | Fabrication method for shielding shell of transformer |
| CN113529063A (en) * | 2020-04-20 | 2021-10-22 | 深圳市海运通电子科技有限公司 | High-temperature-resistant coating aluminum shell treatment method |
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