CN1190518C - Colouring covering film forming method for dluminium material - Google Patents

Colouring covering film forming method for dluminium material Download PDF

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Publication number
CN1190518C
CN1190518C CNB02158463XA CN02158463A CN1190518C CN 1190518 C CN1190518 C CN 1190518C CN B02158463X A CNB02158463X A CN B02158463XA CN 02158463 A CN02158463 A CN 02158463A CN 1190518 C CN1190518 C CN 1190518C
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aluminium
water
aqueous solution
oxysalt
painted
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CN1429928A (en
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平野浩司
溝口佳孝
青木健二
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Kansai Paint Co Ltd
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Kansai Paint Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

The method of forming the colored coating on the aluminum material includes (A) a process for subjecting the aluminum material of aluminum or an aluminum alloy to boehmite treatment by bringing the aluminum material into contact with hot water or steam containing ammonia or amines or not containing them, (B1) a process for subjecting the aluminum material to a first inorganic electrodeposition treatment by dipping it in a first aqueous solution or a first aqueous dispersion, containing at least one of water-soluble or water-dispersible salts of oxo-acids, (C1) an electrolytic coloring process for coloring the aluminum material by depositing metal or a metal oxide by constant direct current electrolysis or alternating current electrolysis by using the aluminum material as a cathode, or (C2) a coloring process for coloring the aluminum material with a dye, and (D) a topcoat coating process for forming a coating on the aluminum material by coating it with a paint.

Description

The colouring covering film formation method of aluminium
Technical field
The present invention relates to a kind of aluminium colouring covering film formation method that forms the good nuisanceless type overlay film of weathering resistance, weather resistance, outward appearance.
Background technology
Past, because the high temperature process excellent performance of aluminum ratio iron and steel etc., so can obtain to have the section bar of various cross-sectional shapes with comparalive ease by hot extrusion.And aluminium is in light weight, be easy to processing, and erosion resistance is good, because these advantageous properties of aluminium itself can be widely used in the fields such as building materials, vehicle component, furniture, can be used as the material relevant with building materials under particularly a lot of situations.
Film formation method as the aluminium that constitutes by aluminum or aluminum alloy, for example, in public clear 56-14753 communique of spy and special public clear 56-24718 communique, disclose from silicate, borate, phosphoric acid salt, chromic salt, molybdate, vanadate, in the aqueous solution or aqueous dispersions of the oxysalt of one or more that select in permanganate and the stannate, the object that will constitute with hot water that contains or do not contain ammonia or amine or aluminum or aluminum alloy that water vapour contacts as anode switch on handle after, utilize the method for electroplating coating acrylic acid or the like melamine class electroplating coating, form adaptation, the overlay film that chemical-resistant and erosion resistance are good.
Recently, be desirable to provide the film formation method of the aluminium of the overlay film that on a kind of basis that is formed on weathering resistance, weather resistance etc., also has good surface appearance.
Past, as the aluminium film formation method that forms the good overlay film of outward appearance, for example, in No. 3202949 communique of special permission (spy opens flat 11-106994 communique), disclose and on aluminum or aluminum alloy, carried out carrying out the electrolytic coloring processing after the anodic oxidation treatment, have on the anodic oxidation overlay film of regulation brightness, implement to electroplate painted aluminium and alloy colouring film formation method by the translucent grey paint that contains a certain amount of white pigment and black pigment, wherein, obtain the grey of Achromatic color, and the kind of coating is constant, can be easily painted goes out the grey from light gray to dark-grey various deep or light degree.
But, form the overlay film that method obtains by above-mentioned colouring covering film, not only do not satisfy the requirement of aspects such as outward appearance, weathering resistance, overlay film adaptation, gloss, L value, and must carry out anodic oxidation treatment, as its treatment solution, owing to adopt reagent such as sulfuric acid, oxalic acid or organic acid-sulfuric acid mixture liquid, so the influence of following the burn into of its treatment unit to dispose waste liquid environment is caused and make nuisancelessization of treatment agent need huge cost.Thereby, need a kind of energy to form the film formation method that except overlay film performances such as weathering resistance, weather resistance, aesthetic appearance, does not also have the overlay film of public hazards.
Summary of the invention
The objective of the invention is to address the above problem, a kind of aluminium colouring covering film formation method that forms the good and non-harmful overlay film of weathering resistance, weather resistance, aesthetic appearance is provided.
That is, in the first string of the present invention, provide a kind of aluminium colouring covering film formation method, it is characterized in that, comprise following operation successively:
(A) make aluminium that constitutes by aluminum or aluminum alloy and the hot water that contains or do not contain ammonia or amine or boehmite treatment process that water vapour contacts,
(B 1) be impregnated into the operation of carrying out the first inorganic electroplating processes in the first at least a aqueous solution of the oxygen acid salt that contains water-soluble or water dispersible or first aqueous dispersions, further preferred, (B 2), containing and operation (B 1) first aqueous solution or second aqueous solution or second aqueous dispersions of the oxysalt that contains of first aqueous dispersions oxysalt of the same race or not of the same race in, further carry out the second inorganic electroplating processes, the operation of switching on repeatedly as required and handling,
(C 1) by carrying out constant current dc electrolysis or alternating current electrolysis with aluminium as negative electrode, precipitating metal or metal oxide carry out painted electrolytic coloring treatment process, perhaps (C 2) utilize dyestuff to the painted painted treatment process of aluminium, and
(D) and then, applying coatings, the finish paint that forms overlay film applies operation.
In second scheme of the present invention, a kind of aluminium colouring covering film formation method is provided, it is characterized in that order is carried out following operation:
(A) make aluminium that constitutes by aluminum or aluminum alloy and the hot water that contains or do not contain ammonia or amine or boehmite treatment process that water vapour contacts,
(C 1) by carrying out constant current dc electrolysis or alternating current electrolysis with aluminium as negative electrode, precipitating metal or metal oxide carry out painted electrolytic coloring treatment process, perhaps (C 2) utilize dyestuff to the painted painted treatment process of aluminium,
(B 1) be impregnated in the first at least a aqueous solution or first aqueous dispersions of the oxygen acid salt that contains water-soluble or water dispersible, carry out the operation of the first inorganic electroplating processes, further preferred, (B 2), containing and operation (B 1) first aqueous solution or second aqueous solution of the oxysalt that contains of first aqueous dispersions oxysalt of the same race or not of the same race or second aqueous dispersions in further carry out the second inorganic electroplating processes, the operation handled of switching on repeatedly as required and
(D) and then, the finish paint that applying coatings forms overlay film applies operation.
Hot-extrudable method as the aluminium forming method in the method for the present invention, usually, heating and the columniform aluminium ingot bar of fusion then, are sent into this melts in the forcing machine, the mould that utilization has the hole of regulation cross-sectional shape pushes, と こ ろ て ん formula To molds the section bar with regulation shape, in order to improve the value of commodity by described hole, it is carried out colorize, give artistry.
Usually, before method of the present invention, as pre-treatment, utilize ordinary method, the aluminium that aluminum or aluminum alloy is constituted carries out degreasing, etch and neutral surface treatment (hereinafter to be referred as surface treatment) in proper order.
Boehmite in the operation of the inventive method (A) is handled, and is to make to utilize conventional method to carry out surface-treated aluminiums such as degreasing, etch, neutralization to contact with hot water that contains or do not contain ammonia or amine or water vapour and carry out.At this moment, handle bath, especially contain in the hot water of ammonia or amine, can add lactic acid or glycerine etc. to increase the thickness of boehmite coating at boehmite.Under any circumstance, the coating that utilizes boehmite to handle formation is preferably tried one's best evenly, on uneven surfaces layer too and the compound overlay film of inorganics of oxysalt also become inhomogeneous, exist in the situation that erosion resistance in the defective part that produces defective, organism overlay film formed thereon on the compound overlay film of this inorganics and chemical-resistant descend.
Below, to the operation (B in the inventive method 1) and (B 2) describe.
Operation (B 1) and operation (B thereafter 2), can be afterwards or operation (C in operation (A) 1) or operation (C 2) carry out afterwards.
By operation (A), operation (C 1) or operation (C 2) aluminium that obtains, must be impregnated into the silicate that contains from water-soluble or water dispersible, borate, phosphoric acid salt, chromic salt, molybdate, vanadate, permanganate, in first aqueous solution or first aqueous dispersions of the oxysalt of one or more that select in tungstate and the stannate, carrying out first energising handles, preferably after this, in second aqueous solution or second aqueous dispersions that contain the oxysalt that contains with the first above-mentioned aqueous solution or first aqueous dispersions oxysalt of the same race or not of the same race, further to the aluminium that the is obtained processing of switching on, carry out the second inorganic electroplating processes, and then can carry out aforementioned energising as required repeatedly and handle.
Like this, by the processing of in the oxysalt aqueous solution or aqueous dispersions, switching on, form on the surface of aluminium, change into the inorganic overlay film of the densification that overlay film-oxysalt or boehmite overlay film-oxysalt constitute by oxysalt.Yet, utilize an energising in the oxysalt water bath to handle, therefore the active site of the aluminium that can not be covered fully, becomes for example produce the reason that corrosion etc. is separated out unusually on this aluminium.Therefore, by with oxysalt water bath for the first time of the same race or not of the same race in the processing of further switching on repeatedly, obtain finer and close inorganic overlay film, and under the situation of mixing oxysalt, even produce the combination of sedimentary oxysalt kind, by respectively to they processing of switching on repeatedly, the oxysalt of any kind of all can be separated out on aluminium, obtains chemical-resistant, erosion resistance and finish paint and applies adaptability, adaptation than handle the better inorganic compounding overlay film of overlay film that obtains by energising in oxysalt water bath once.
As the example of oxygen acid salt,, comprise that general formula is M as silicate 2OxSiO 2(M represents basic metal, alkanolamine, alkanolamine quaternary ammonium or guanidine etc. to the various silicate of expression.X is the positive number of 0.5-20.)。As an alkali metal salt, use water glass, potassium silicate, lithium silicates etc. as ammonium salt, use silicic acid tri ethanol ammonium salt etc., and guanidine silicate etc. are various water-soluble or be partially soluble in the silicate of water.As borate, can enumerate lithium metaborate (LiBO 22H 2O), lithium tetraborate (Li 2B 4O 75H 2O), sodium metaborate (NaBO 2), sodium tetraborate (Na 2B 4O 710H 2O), sodium pentaborate (NaB 5O 810H 2O), Sodium peroxoborate (NaBO 2H 2O 23H 2O), Sodium Tetraborate hydrogen peroxide adduct (Na 2B 4O 7H 2O 29H 2O), potassium metaborate (KBO 2), potassium tetraborate (K 2B 4O 75H 2O), tetraboric acid ammonium [(NH 4) 2B 4O 74H 2O] etc., as phosphoric acid salt, can enumerate with the Sodium hexametaphosphate 99 is the general formula (NaPO of representative a) nThe various sodium-metaphosphates of (n is the integer of 2-14) expression as chromic salt, can be enumerated lithium chromate (Li 2CrO 42H 2O), Sodium chromate (Na 2CrO 410H 2O), potassiumchromate (K 2CrO 4), ammonium chromate [(NH 4) 2CrO 4], yellow ultramarine (CaCrO 42H 2O), strontium yellow (SrCrO 4) etc., as molybdate, can enumerate general formula xM 2OyMoO 3NH 2(M is Li to O, Na, K or NH 4, x is the integer of 1-5, y is the integer of 1-12, n be 0 or positive integer) the various molybdates of expression, ortho-molybdic acid lithium (Li for example 2MoO 4), ortho-molybdic acid sodium (Na 2MoO 4), ortho-molybdic acid potassium (K 2MoO 45H 2O), ammonium paramolybdate [(NH 4) 6Mo 7O 244H 2O], 12-sodium phosphomolybdate [Na 3(PO 4Mo 12O 36) 10H 2O] etc., as vanadate, can enumerate ortho-vanadic acid lithium (Li 3VO 4), sodium orthovanadate (Na 3VO 4), lithium metavanadate (LiVO 32H 2O), sodium metavanadate (NaVO 34H 2O), potassium metavanadate (KVO 3), ammonium meta-vanadate [(NH 4) VO 3], sodium pyrovanadate (Na 4V 2O 7) etc., as permanganate, can enumerate sodium permanganate (NaMnO 4SH 2O), potassium permanganate (KMnO 4), ammonium permanganate [(NH 4) MnO 4] etc., as tungstate, can enumerate formula M 2OWO 3(M represents Li, Na, K or (NH 4) etc.) the ortho-tungstic acid salt of expression, sodium wolframate (Na for example 2WO 42H 2O) etc., formula M 2O4WO 3(M represents Li, Na, K or (NH 4) etc.) metatungstate of expression, metatungstic acid sodium (Na for example 2W 4O 13) etc., general formula 5M 2O12WO 3The para-tungstate of (M is the same) expression, for example sodium paratungstate (Na 10W 12O 41) etc., five ammonium tungstate [(NH 4) 4W 5O 175H 2O], seven ammonium tungstate [(NH 4) 6W 7O 246H 2O], Tungstophosphoric acid, sodium salt (Na 3PO 412WO 318H 2O), barium borotungstate Ba 9[B (W 2O 7) 6] 2Deng, as stannate, can enumerate sodium metastannate (SnO 2MH 2OnNaOH), metastannic acid potassium (SnO 3MH 2OnKOH) representational example such as (m in two formulas is 0 or positive number, and n is a positive number).These water-soluble or water dispersible oxysalts can use separately, perhaps, if can not produce precipitation etc. owing to mutual reaction, use simultaneously that two or more also it doesn't matter.Under any circumstance, the concentration in the oxysalt aqueous solution is below the saturation concentration, get final product more than the 0.1 weight %.
Energising is handled, and the aluminium that boehmite can be handled is impregnated in the water bath of above-mentioned water-soluble or water dispersible oxysalt, is that electrode is handled according to common electro dipping method with it.At this moment, can adopt direct current, alternative any one, adopt under the situation of direct current, be the anode processing of switching on aluminium.For example, in the constant voltage electrochemical plating, applying certain voltage between anode and negative electrode switches on, after the violent decline of the current value that is accompanied by overlay film formation, current value reaches certain value, and then can continue energising, in addition, in constant current plating method, to have the mode of certain current density with respect to male or female, make the voltage that applies of anode and negative electrode change continuously, switch on, after sharply rising through the voltage that is accompanied by overlay film formation, voltage reaches certain value, and then can continue energising.Certainly in aforesaid operations, after arriving certain current value or certain magnitude of voltage, handle even proceed the successive energising, do not hinder yet.And the voltage that applies is preferably 5～200 volts when direct current, is preferably 5～100 volts when exchanging, and by making voltage in this scope, can form the continuous overlay film of oxysalt reliably on aluminium.And, fully can be not destroyed in order to make formed continuous overlay film, can form reliably and have the excellent erosion resistance and the compound overlay film of inorganics of chemical-resistant.And, can not freeze corresponding to the kind of water-soluble oxysalt etc., can the ebullient scope yet in, can suitably determine the fluid temperature when energising is handled, can in 10～40 ℃ scope, advantageously implement usually.Further in the oxysalt water bath, switch on after separating out oxysalt under the situation about handling utilizing above-mentioned processing, if oxygen acid salt bath of the same race, then do not wash directly and carry out, if oxysalt not of the same race particularly if produce sedimentary combination, is then washed immediately, removal is attached to lip-deep oxysalt of separating out at last, afterwards, be impregnated in the oxysalt water bath of the same race or not of the same race the processing of switching on once more.And then, can carry out aforementioned energising as required repeatedly and handle.Like this, on aluminium material surface, form inorganic overlay film, also can after energising is handled, wash immediately, if necessary, carry out drying room temperature to 260 ℃, preferred 150～260 ℃, carry out after further improving erosion resistance, chemical-resistant, weather resistance and the tack of inorganic overlay film.
Below to the operation (C of the inventive method 1) describe.
In the method for the invention, carry out the operation (C that electrolytic coloring is handled 1), can be at operation (A), operation (B 1) or operation (B 2) carry out afterwards.
Electrolytic coloring operation (the C of method of the present invention 1), by with by operation (A), operation (B 1) or operation (B 2) aluminium that obtains carries out constant current dc electrolysis or alternating current electrolysis as negative electrode, precipitating metal or metal oxide, carry out painted.
It is by providing negative direct current or interchange to carry out to aluminium in containing the solution of metal-salt that electrolytic coloring is handled.As interchange, except commercial ac power, can adopt sine wave, rectangular wave, choppy sea, saw shape ripple or with the alternating-current of their similar waveforms.Electrolytic coloring is handled and also can be utilized constant voltage process to carry out, but from reducing the angle of overlay film thickness deviation, preferably adopts constant current anodizing process.
Electrolytic coloring is handled and to be performed such, that is, and for example in the aqueous solution that contains single nickel salt, rose vitriol, copper sulfate, stannous sulfate etc., by operation (A), operation (B 1) or operation (B 2) aluminium that obtains and by nickel plate or stainless steel plate constitute between the utmost point, pass to interchange, direct current or pulsed current.
Below, illustrate that the dyestuff that utilizes of the inventive method carries out the operation (C of painted painted processing 2).
In the method for the invention, above-mentioned operation (C 2) can be at operation (A), operation (B 1) or operation (B 2) carry out afterwards.
Kind as the dyestuff that in above-mentioned painted processing, uses, it can be existing known water-soluble dye, also can be oil-soluble colourant, for example, in the classification of dye structure, can enumerate (I) azoic dyestuff class, (II) anthraquinone dye group, (III) indigoide colors class, (IV) solubility and build dye class, (V) thioxine dyes class, (VI) carbonium dye class, (VII) quinonimine dye class, (VIII) phthalocyanine pigment class etc.The concentration of employed dyestuff can be used in the scope of 0.001 weight %～10 weight %, preferably in the scope of 0.01 weight %～5 weight %.
More particularly, the known Alfast Yellow of trade(brand)name SW-5101 as the manufacturing of オ リ エ Application ト chemical industry Co., Ltd., Alfast Orange SW-5201, Alfast OrangeSW-5202, Alfast Orange SW-5203, Alfast Red SW-5301, Alfast BrownSW-5401, Alfast Brown 5402, Alfast Blue SW-5601, Alfast BlueSW-5602, Alfast Black SW-5801, Alfast Black SW-5802, dyestuffs such as AlfastBlack5803 are in photostabilization, aspects such as weathering resistance are preferred.
As concrete coloring treatment process, for example adopt following method, will be by operation (A), operation (B 1) or operation (B 2) aluminium that obtains, be impregnated into and be dissolved in above-mentioned dyestuff in the de-salted water and dye strength is in the solution of 0.1～1.0 weight %, at dyeing temperature is that 55～60 ℃, dyeing time are that 2～40 minutes, pH value are to dye under 4～10 the condition, washes then, drying.At this, how many optimum values of pH understands some because of the difference of dyestuff kind changes, but the pH value as required, can utilize acetic acid, sodium-acetate or caustic soda to carry out suitable adjusting in 4～10 scope usually.
Below, illustrate that the finish paint that applies coating, forms overlay film applies operation (D).
The operation of the inventive method (D) is at operation (C 1) or operation (C 2), operation (B 1) or operation (B 2) carry out afterwards.
The coating that in operation (D), uses, can use existing various coating, for example can enumerate powder coating, organic solvent class sprayed coating, the water-based sprayed coating, cation electroplating paint, anion electroplating paint etc., for anion electroplating paint wherein, can the vinyl-based copolymer resins of carboxyl will be contained, melamine resin, solidifying agent such as blocked isocyanate, and then also has pigment, dyestuff, solidify catalyst, flow modifier, UV light absorber etc. cooperate, by adding neutralizing agent (diethylamine for example, triethylamine etc.) carboxyl of vinyl-based copolymer resins is carried out after the water-dispersion, add deionized water, obtain the solid anion electroplating paint that is divided into 5 weight %～20 weight % that forms.
Using such anion electroplating paint to form in the process of filming, make anion electroplating paint as bath, after in this is bathed, flooding aluminium, form the anion electroplating japanning of the dry film thickness of about 5～30 μ m, do not wash (no rinsing) or wash (rinsing), then, at room temperature be cured (セ Star テ Application グ) afterwards, film by firing (for example under about 160～200 ℃, carrying out about 20～40 minutes) formation.
Description of drawings
Fig. 1 is the synoptic diagram that is used to illustrate an example of existing colouring covering film formation method.
Fig. 2 is the synoptic diagram that is used to illustrate first kind of form of implementation of the inventive method.
Fig. 3 is the synoptic diagram that is used to illustrate second kind of form of implementation of the inventive method.
Embodiment
Below, the present invention will be described in more detail with embodiment.Embodiment does not play the qualification effect to the present invention.In addition, " part " and " % " expression " weight part " and " weight % ".
Production Example 1 (Production Example of anion electroplating paint)
In reaction vessel, add Virahol 70g, remain on 80 ℃, to wherein adding vinylbenzene 10g, methyl methacrylate 31g, n-butyl acrylate 10g, ethyl propenoate 30g, vinylformic acid 2-hydroxyl ethyl ester 12g, vinylformic acid 7g and azo two (methyl pentane nitrile) 1g, kept one hour down at 80 ℃, react, make acrylic acid or the like copolymer resins (a).This acrylic acid or the like copolymer resins (a) weight-average molecular weight is about 20,000, acid number is that 55mgKOH/g, hydroxyl value are 58mgKOH/g.
As mentioned above, carboxyl with respect to acrylic acid or the like copolymer resins (a) 70 parts (solids components) cooperates 0.4 normal triethylamine, afterwards, carry out blending dispersion, then, to blending dispersion ニ カ ラ Star Network MX600 wherein (three and Chemical Co., Ltd. make, trade(brand)name Block ト キization メ ラ ミ Application resin) after 30 part, slowly drip deionized water while stirring, and then interpolation triethylamine, making the pH value is 7.5, the emulsion that the anion electroplating paint of the enamel paint class of acquisition solids component 10% is used.
Acrylic acid or the like dispersion resin (the molecular weight 2 of the carboxylic acid add-on type of interpolation 55%, 000, acid number 55mgKOH/g, pigment dispersing resin) 5.45 parts, CR-93 (Ishihara Sangyo Kaisha, Ltd.'s system, trade(brand)name チ Application is white) 25 parts, 0.5 part of triethylamine, 25.05 parts of deionized waters, the pigment paste A of acquisition solids component 50%.
As mentioned above, cooperate pigment paste A6.2 part in the emulsion 10% 1000 parts (100 parts of solids components), and then, add triethylamine, making the pH value is 8.5, adds deionized water, obtains the anion electroplating paint of solids component 10%.
Production Example 2
(Production Example of cation electroplating paint)
In reaction vessel, add 27 parts of 27 parts of propyl carbinols and Virahols, be heated to 90 ℃.To wherein with about two hours 30 parts of time drip styrenes, 35 parts of methacrylic acid 2-ethylhexyls, 20 parts of vinylformic acid 2-hydroxyl ethyl esters, N, the mixture of 15 parts of N-dimethylaminoethyl acrylate, 3.5 parts of Diisopropyl azodicarboxylates.Be reflected under the condition of injecting nitrogen and carry out.Temperature of reaction remains on 90 ℃, carries out 4 hours reaction again, obtains solids component as matrix resin and be 65% acrylic resin.
In another container, in 40 parts of methyl ketoximes, dripping 50 parts of isophorone diisocyanates (IPDI) under 40～60 ℃ the temperature, afterwards,, obtain solidifying agent (end-blocking) polyisocyanate compounds of solids component 90% 80 ℃ of heating one hour.
As mentioned above, 65% acrylic resin 107.7 parts (70 parts of solids components), (end-blocking) polyisocyanate compounds 33.3 parts (30 parts of solids components), liquid organotin 2.5 parts (1 part of solids component), 10% formic acid are being cooperated for 8.2 parts, after evenly stirring, powerful on one side the stirring on one side with dripping 163.9 parts of deionized waters, the emulsion that the cation electroplating of acquisition solids component 32.0% is used in about 15 minutes.
As mentioned above, add 32% cation electroplating with 186.5 parts of emulsion 318.5 parts (101 parts of solids components), pure water, obtain the cation electroplating paint of solids component 20%.
Embodiment 1
To thickness is the aluminium alloy plate (6063) of 1.5mm, use ラ イ ト Network リ-Application D11 (trade(brand)name of 3% in turn, common prosperity society chemistry society makes) the weakly alkaline grease-removing agent 75 ℃ handle down 5 minutes with degreasing, use 10% sodium hydroxide 0 ℃ of following etch 3 minutes and 30 seconds, carry out neutral surface treatment in two minutes with 20% sulfuric acid then.
Aluminium alloy plate after the surface treatment is impregnated in the boiled water of deionized water of 10 μ Ω/cm after 10 minutes, takes out, wash with boehmite and handle.
Then, with the water glass (Na of this aluminium alloy plate as anode pickling to 10% 2O2SiO 2) in the aqueous solution, after 30 volts of energisings 60 seconds, wash, 160 ℃ dry 30 minutes down, carry out the first inorganic electroplating processes.
The aluminium alloy plate that will carry out after the above-mentioned first inorganic electroplating processes is connected on the negative electrode, applies the voltage of 25V in the aqueous solution that contains single nickel salt 100g/L, boric acid 40g/L, carries out electrolytic coloring and handles, to carry out the electrolytic coloring treatment process.
On the aluminium alloy plate after carrying out the electrolytic coloring treatment process, use the anion electroplating paint that obtains by Production Example 1 to electroplate the painted operation,, obtain aluminium No.1 by under 180 ℃, carrying out 20 minutes fire.
Embodiment 2
Except before the first inorganic electroplating processes operation of embodiment 1, carrying out the electrolytic coloring treatment process, identical with embodiment 1, obtain aluminium No.2.
Embodiment 3
After the first inorganic electroplating processes operation in embodiment 2, be impregnated into 3% sodium metaborate (NaBO 2) in, similarly, after 60 volts of energisings 60 seconds, wash, drying is 30 minutes under 160 ℃, carries out the second inorganic electroplating processes, and is in addition identical with embodiment 2, obtains aluminium No.3.
Embodiment 4
On the aluminium alloy plate that the electrolytic coloring that carries out embodiment 1 is handled, be coated in the cation electroplating paint that obtains in the Production Example 2, the operation that forms overlay film,, obtain aluminium No.4. by under 180 ℃ temperature, firing 20 minutes
Comparative example 1
Surface treated aluminium alloy plate replaces boehmite to handle, in 20 ℃ aqueous sulfuric acids (150g/L), with 100A/m similarly to Example 1 2Current density carry out 35 minutes anodic oxidation treatment, generate the anodic oxidation overlay film of thickness 9 μ m.
Then, the aluminium alloy plate of antianode oxide treatment carries out the electrolytic coloring identical with embodiment 1 and handles.
Then, with 65 ℃ warm water the rinsing (sealing of hole) that the aluminium alloy plate that carries out the electrolytic coloring processing carried out 2 minutes is handled.
Then, carry out the plating japanning identical, obtain aluminium No.5 with embodiment 1.
Comparative example 2
Replace the anodic oxidation treatment of comparative example 1, carry out following anodic oxidation treatment, that is, go up and in electrolytic bath, adopt 15% sulphuric acid soln that remains on 20 ℃, at current density 1.4A/dm 2Down, carry out 48 minutes anodic oxidation, form the anodic oxidation overlay film of thickness 20 μ m, in addition, carry out the processing identical, obtain aluminium No.6 with comparative example 1.
Aluminium No.1～6 that obtained are made a service test.The result is illustrated in the table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Comparative example 1 Comparative example 2
Aluminium No.1 No.2 No.3 No.4 No.5 No.6
Be coated with face smoothness (annotating 1) ○ ○ ○ ○ ○ ○
Outward appearance (annotating 2) ○ ○ ○ ○ △ △
Promote weathering resistance (annotating 3) 90 91 93 90 81 83
The adaptation of filming (annotating 4) ○ ○ ○ ○ △ △
Gloss (annotating 5) 120 121 119 120 112 110
L value (annotating 6) 87 86 88 86 80 81
Method for testing performance
(annotate 1) is coated with the face smoothness: estimate with visual observation film coated surface (elephant skin, concavo-convex etc.).
Estimate: visual
Zero: good
△: slightly bad
*: bad
(annotating 2) outward appearance: the disguise of estimating the mould marking.
Estimate: visual
Zero: good
△: slightly bad
*: bad
(annotating 3) promotes weathering resistance (gloss retention %): adopt サ Application シ ヤ イ Application ウ エ ザ オ メ--(ス ガ trier).Gloss retention=through the specular reflectance of filming before the specular reflectance/test of filming afterwards in 2000 hours) * 100, adopt JIS K-5400 60 degree specular reflectances to measure the specular reflectance of filming.
(annotate 4) adaptation of filming: at 40 ℃ down on each steel plate of 240 hours of dipping, cut out grid, paste and peel off セ ロ テ-プ (registered trademark of ニ チ バ Application Co., Ltd.) with cutting knife.
Zero: not unusual
△: a part of filming is stripped from
*: film and peel off
(annotate 5) gloss: according to the 60 degree mirror surface lusters of JIS K-5400 7.6 (1990), measuring input angle and be subjected to firing angle to be respectively 60 reflectivity when spending, is that 100 o'clock percentage is represented the gloss intensity of filming with the glossiness of the reference plane of mirror surface luster.
(annotating 6) L value: use angle spectrophotometer ミ ノ Le CR-300 (ミ ノ Le society makes, trade(brand)name, spectrophotometer) to measure.
In existing aluminium treatment process, produce sulfuric acid waste in the anodic oxidation treatment, fog, it is handled and operation is attended by danger, but employing the present invention, in this technology, there is not this problem, be non-harmful, outward appearance, weathering resistance, the adaptation of filming, gloss, film performances such as weather resistance are good, simultaneously, the coating of using as facial ornament coating, if adopt existing anonizing, when cation electroplating paint is painted as facial ornament, destroyed the oxidation overlay film of aluminium, and, under the situation that adopts sprayed coating, because tack is insufficient, so only limit to anion electroplating paint, but the present invention can carry out cation electroplating paint, powder coating, the sprayed coating of organic solvent type, performance has been widened in the coating of various coating such as water-based sprayed coating, outward appearance, the scope of finishability etc.

Claims (7)

1, a kind of formation method of aluminium colouring covering film is characterized in that, order is carried out following operation:
(A) make aluminium that constitutes by aluminum or aluminum alloy and the hot water that contains or do not contain ammonia or amine or boehmite treatment process that water vapour contacts,
(B 1) be impregnated into the operation of carrying out the first inorganic electroplating processes in the first at least a aqueous solution of the oxygen acid salt that contains water-soluble or water dispersible or first aqueous dispersions,
(C 1) by carrying out the constant current dc electrolysis with aluminium as negative electrode or alternating current electrolysis, precipitating metal or metal oxide carry out painted electrolytic coloring treatment process, perhaps (C 2) utilize dyestuff to the painted painted treatment process of aluminium, and
(D) and then, applying coatings applies operation with the finish paint that forms overlay film.
2, colouring covering film formation method as claimed in claim 1 further comprises following operation: (B 2) at operation (B 1) afterwards, containing and operation (B 1) first aqueous solution or second aqueous solution or second aqueous dispersions of the oxysalt that contains of first aqueous dispersions oxysalt of the same race or not of the same race in, further carry out the second inorganic electroplating processes, the processing of switching on repeatedly as required.
3, colouring covering film formation method as claimed in claim 1 or 2, described oxygen acid salt is selected from silicate, borate, phosphoric acid salt, chromic salt, molybdate, vanadate, permanganate, tungstate and stannate.
4, a kind of aluminium colouring covering film formation method is characterized in that, order is carried out following operation:
(A) make aluminium that constitutes by aluminum or aluminum alloy and the hot water that contains or do not contain ammonia or amine or boehmite treatment process that water vapour contacts,
(C 1) by carrying out the constant current dc electrolysis with aluminium as negative electrode or alternating current electrolysis, precipitating metal or metal oxide carry out painted electrolytic coloring treatment process, perhaps (C 2) utilize dyestuff to the painted painted treatment process of aluminium,
(B 1) be impregnated into the operation of carrying out the first inorganic electroplating processes in the first at least a aqueous solution of the oxygen acid salt that contains water-soluble or water dispersible or first aqueous dispersions,
(D) and then, applying coatings applies operation with the finish paint that forms overlay film.
5, colouring covering film formation method as claimed in claim 4 further comprises following operation: (B 2) at operation (B 1) afterwards, containing and operation (B 1) first aqueous solution or second aqueous solution or second aqueous dispersions of the oxysalt that contains of first aqueous dispersions oxysalt of the same race or not of the same race in, further carry out the second inorganic electroplating processes, the processing of switching on repeatedly as required.
6, as claim 4 or 5 described colouring covering film formation methods, described oxygen acid salt is selected from silicate, borate, phosphoric acid salt, chromic salt, molybdate, vanadate, permanganate, tungstate and stannate.
7, utilize the aluminium that obtains as any one described method in the claim 1～6.
CNB02158463XA 2001-12-27 2002-12-26 Colouring covering film forming method for dluminium material Expired - Fee Related CN1190518C (en)

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CN1920111B (en) * 2006-07-25 2011-08-10 台山市金桥铝型材厂有限公司 Composite coloration method of aluminium anode oxide film
CN1920112B (en) * 2006-07-26 2010-12-08 李文英 Dyeing dip-coating composite processing method of aluminium section bar surface
KR101195458B1 (en) * 2009-04-22 2012-10-30 한양대학교 에리카산학협력단 Method for treating the surface of metal
KR101274978B1 (en) * 2010-04-21 2013-06-14 한양대학교 에리카산학협력단 Method for surface treatment to manufacture aluminium material with high strength and black color
TWI575113B (en) * 2012-02-21 2017-03-21 Catcher Technology Co Ltd Methods of white coloring on the surface of metallic materials
JP6909582B2 (en) * 2017-01-18 2021-07-28 株式会社Ｊｃｕ Coloring plating solution and coloring method
CN108093591A (en) * 2017-11-20 2018-05-29 广东欧珀移动通信有限公司 Plate and preparation method thereof, mobile terminal shell, mobile terminal
CN113151876B (en) * 2021-04-20 2022-05-06 深圳市曼特表面处理科技有限公司 Stabilizing agent for aluminum alloy anodic dyeing and preparation method thereof
WO2023048342A1 (en) * 2021-09-27 2023-03-30 문정일 Method for manufacturing ceramic coating layer for aluminum material, and aluminum material cookware manufactured using same
CN114775012A (en) * 2022-05-05 2022-07-22 湖北蓝华铝业有限公司 Surface coloring agent for aluminum alloy processing

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