CN1353296A - Method of manufacturing aluminium radiator fin material and aluminium radiator fin made by said method - Google Patents
Method of manufacturing aluminium radiator fin material and aluminium radiator fin made by said method Download PDFInfo
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- CN1353296A CN1353296A CN01137459A CN01137459A CN1353296A CN 1353296 A CN1353296 A CN 1353296A CN 01137459 A CN01137459 A CN 01137459A CN 01137459 A CN01137459 A CN 01137459A CN 1353296 A CN1353296 A CN 1353296A
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
- F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/20—Orthophosphates containing aluminium cations
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/82—After-treatment
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/081—Heat exchange elements made from metals or metal alloys
- F28F21/084—Heat exchange elements made from metals or metal alloys from aluminium or aluminium alloys
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Chemical Treatment Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
In the process where an aluminum base material for a fin material is subjected to conversion treatment, a chemical conversion coating is deposited while maintaining a conversion treatment solution to the following compositional ranges under the conditions of the solution temperature of 30 to 70 deg.C and the treatment time of 1 to 10 sec. The surface of the chemical conversion coating is deposited with a corrosion resistant coating and/or a hydrophilized coating composed of water based resin: zirconium ions of 10 to 10,000 ppm, phosphoric ions of 10 to 10,000 ppm, aluminum ions of 100 to 10,000 ppm, effective fluorine ions of 1 to 500 ppm, organic acid having one or more phenolic hydroxyl groups in the molecule of 10 to 10,000 ppm, and pH of 1.0 to 4.0.
Description
Technical field
The present invention relates to a kind of manufacture method and hydrophilic aluminium radiator fin material obtained by this method that improves corrosion resistance and fusible aluminium radiator fin material (aluminumfin material) that have.
Background technology
Aluminium and aluminum alloy materials are lightweights and have good processability and thermal conductivity so, make them can be widely used as the element of heat exchanger such as automobile and room air conditioner.Especially in the heat-exchanging part of machine, use the aluminium radiator fin material in many cases.
When the air-conditioner that described fin material is housed moved with the type of cooling, the aqueous vapor in the atmosphere can condensation on the surface of fin material, stopped up thereby form between fin, had so just weakened cooling capacity.In order to eliminate this water condensation, usually hydrophily is carried out on the surface of fin and handle.Although there is the method for the surface of fin being carried out water-proofing treatment, adopt this method, a large amount of water droplets that caused by waterproofing agent can form obstruction between fin, thereby make cooling capacity that sizable weakening be arranged, and therefore this method is seldom used now.
Although it is essential as mentioned above the hydrophily on fin material surface being handled, this hydrophily processing can make the water-wet that is condensed all the time of the surface of fin.Therefore, the water that sees through hydrophilic coating forms oxygen concentration cell between fin material and soldering flux, thereby causes the metal erosion reaction, and perhaps contained atmosphere pollution generation hydration and metal erosion reacted in infiltration water.The corrosion product that this reaction forms gathers together on the surface of fin, thereby has weakened heat-exchange capacity.When moving with heater mode, equally also have problems, promptly corrosion product becomes white dust, and it is discharged in the room from blower fan with hot blast.
In order to overcome the problems referred to above, day disclosure communique is flat-and 5-125555 disclosed a kind of fin material of precoating, it is made through following method, on aluminium base, form and contain the alkaline silicate of special ratios and the hydrophilic coating of hydrophilic polymer, wherein on base material, form chromate-chromate and handle the coating of (chromating), the then above-mentioned hydrophilic coating of heat drying.
The general introduction of invention
Although above-mentioned day disclosure communique flat-adopt chromate-chromate to handle among the 5-125555, from the angle of environment, better be the chemical conversion treating agent that uses chromate-free basically.When adopting phosphate-chromate to handle, after handling, chemical conversion must wash, remain on the coating to prevent Cr VI, but the waste water that contains chromium that causes with the disposal washing can cause the another one problem.Yet, and do not know to adopt the processing method of the chromate-free inorganic agent that can form fin material with enough corrosion resistances and moisture resistivity.Therefore, the purpose of this invention is to provide a kind of method of using the chromate-free chemical conversion treating agent to make the aluminium radiator fin material, this method is favourable to environment, can satisfy required performance characteristic such as corrosion resistance and moisture resistivity simultaneously, and aluminium radiator fin material obtained by this method is provided.
The manufacture method of aluminium radiator fin material of the present invention comprises, in the chemical conversion treatment step of aluminium base, form chemical conversion coating (chemical conversion coat), the hydrophilic coating that on this chemical conversion coating, forms erosion shield and/or form by water-base resin
Described chemical conversion coating is that the composition with the chemical conversion Treatment Solution remains in the following ranges and is in that to make solution temperature be that 30-70 ℃ and processing time are to obtain under the 1-10 condition of second.
Zirconium ion 10-10,000ppm
Phosphate anion 10-10,000ppm
Aluminium ion 100-10,000ppm
Effective fluorine ion (fluoride ion) 1-500ppm
The organic acid 10-10 that in molecule, contains at least one phenol type hydroxyl, 000ppm
PH value 1.0-4.0
The described organic acid that contains at least one phenol type hydroxyl in molecule comprises at least a material that is selected from phenol, phenolsulfonic acid, tannic acid and its derivative.
After forming described chemical conversion coating, do not wash and with the roll-in branch that anhydrates, the hydrophilic coating that forms erosion shield subsequently and/or form by water-base resin.
The invention still further relates to the aluminium radiator fin material of making by above-mentioned any method.The chemical conversion coating of product aluminium radiator fin material better comprises zirconium and phosphorus, and their amount is respectively 1-100mg/m
2
The detailed description of invention
Below the present invention is described in detail.
The described aluminium radiator fin material of specification of the present invention is a kind of material that is used to form heat exchanger fin.This fin material is a kind of sheet aluminium sheet of ring-type or with the rolled-up aluminium alloy of coiled type, it randomly makes through following method, and it is carried out ungrease treatment, carries out chemical conversion subsequently and handles, form erosion shield and/or, give its hydrophily by the hydrophilic coating that water-base resin is formed.The fin material that forms chemical conversion coating and erosion shield and/or hydrophilic coating is by this way thereon cut, process and be assembled into heat exchanger.
In the manufacture method of aluminium radiator fin material of the present invention, at first the aluminum or aluminum alloy plate is carried out degreasing when needed.The ungrease treatment method comprises the alkali degreasing that uses the solvent degreasing that gasoline or n-hexane carry out and use the alkaline solution that comprises NaOH, sodium metasilicate or sodium phosphate to carry out.Can suitably select processing method by the condition of aluminum.
In chemical conversion treatment step subsequently, spray fin material with the chemical conversion Treatment Solution.The inject process time, even the duration that the chemical conversion Treatment Solution contacts with fin material is 1-10 second, and treatment temperature (solution temperature) is 30-70 ℃, is preferably 40-60 ℃.If the above-mentioned processing time is less than 1 second, then can not form the chemical conversion coating of capacity.On the other hand, though when the time that handle more than 10 seconds, but the estimated performance feature does not have further improvement, and this also is disadvantageous from the angle of cost.If treatment temperature is lower than 30 ℃, then the reactivity of chemical conversion treating agent is too low, to such an extent as to can not form the chemical conversion coating of capacity.On the other hand, even when handling being higher than 70 ℃, but the estimated performance feature does not have further improvement, and this also is disadvantageous from the angle of cost.In practice of the present invention, can adopt dipping or other technology to replace described inject process.
The composition of used chemical conversion Treatment Solution is in above-mentioned chemical conversion is handled: zirconium ion 10-10, and 000ppm is preferably 100-1,000ppm; Phosphate anion 10-10,000ppm is preferably 100-1,000ppm; Aluminium ion 100-10,000ppm is preferably 500-5,000ppm; Effectively fluorine ion 1-500ppm is preferably 1-10ppm; Contain the organic acid 10-10 of at least one phenol type hydroxyl in molecule, 000ppm is preferably 100-1,000ppm; The pH value is 1.0-4.0, is preferably 1.5-2.5.
Above-mentioned zirconium ion is by the fluorine zirconic acid, the lithium of fluorine zirconic acid, sodium, potassium, ammonium and other salt, and zirconium sulfate, zirconium nitrate, zirconyl nitrate, zirconium fluoride waits provides.If the amount of zirconium ion is less than 10ppm, then the zirconium ion content in the gained chemical conversion coating is too low, to such an extent as to can not give the hydrophilic coating film with corrosion resistance and cohesive.If this amount surpasses 10,000ppm, but then the estimated performance feature does not have improvement, and this also is disadvantageous from the angle of cost.
Can provide phosphate anion by adding phosphate cpd, described phosphate cpd is selected from phosphoric acid, ammonium phosphate, alkali metal phosphate such as sodium phosphate, potassium phosphate etc., alkali earth metal phosphate such as calcium phosphate, magnesium phosphate etc. and condensed phosphoric acid.If the amount of phosphate anion is less than 10ppm, then the phosphate anion content in the gained chemical conversion coating is too low, to such an extent as to can not give corrosion resistance.If this amount surpasses 10,000ppm, but then the estimated performance feature does not have improvement, and easily form mud.
Above-mentioned aluminium ion is waited by aluminum fluoride, aluminium oxide, aluminum sulfate, alum, alumina silicate, aluminate such as sodium aluminate etc. and fluoaluminate such as cryolite and provides.Aluminium ion also can be provided by the aluminium radiator fin material.If aluminum ions amount less than 100ppm, then can not promote the reaction of chemical conversion coating, thereby weaken corrosion resistance that if this amount surpasses 10,000ppm then hinders the formation of chemical conversion coating, but can form mud in the chemical conversion Treatment Solution on the contrary.
Above-mentioned effective fluorine ion can be by hydrofluoric acid, ammonium fluoride, hydrofluorination ammonium, sodium fluoride, sodium hydro-fluoride waits provides, when the compound that uses fluoride such as fluorine zirconic acid or ammonium fluozirconate were given body as above-mentioned zirconium ion, fluorine ion also can provide a part to body by this zirconium ion.Effectively fluorine ion is meant fluorinion concentration free in Treatment Solution.Can measure effective fluorinion concentration with apparatus measures Treatment Solution with fluoride ion electrode.If effectively the amount of fluorine ion is less than 1ppm, then the inadequate corrosion in surface can't form the chemical conversion coating of capacity to fin material.If this amount surpasses 500ppm, then the aluminium ion concentration in the chemical conversion Treatment Solution is owing to excessive corrosion (overetching) surpasses scope of the present invention, thereby obstruction is reacted and formed a large amount of mud.
In order further to improve corrosion resistance and moisture resistivity, Treatment Solution of the present invention is included in the organic acid that contains at least one phenol type hydroxyl in the molecule, and its concentration is 10-10,000ppm.If this amount is less than 10ppm, because the amount that adds is not enough, so can on performance characteristic, not obtain to improve fully.If this amount surpasses 10,000ppm then can not obtain further to improve on performance characteristic.Organic acid comprises phenol, tannic acid and phenolsulfonic acid preferably.
If the pH value of described chemical conversion Treatment Solution is lower than 1.0, then excessive corrosion can make the formation of chemical conversion coating become difficult, thereby has weakened corrosion resistance.If this value surpasses 4.0, then chemical conversion coating is difficult to form, and has so also weakened corrosion resistance.The composition of analytical chemistry conversion processing solution uses a certain concentrated solution, and the composition of solution is adjusted in the scope of the present invention.
Treatment Solution can comprise other additive, for example known inhibitor such as molybdic acid and wolframic acid, metal ion such as titanium, nickel, vanadium, hafnium, iron and zinc, and chemical conversion accelerator such as nitrite and hydrogen peroxide, and be used to keep aluminum ions chelating agent.
Wash about 2-10 second with water to having experienced the aluminium radiator fin material that above-mentioned chemical conversion handles, or push with removal moisture with rubber rollers etc.Use in the present invention under the situation of chemical conversion Treatment Solution, it is just enough to squeeze the water out with rubber rollers etc., need not washing, and remaining chemical conversion Treatment Solution can not produce adverse influence to step subsequently, can not improve corrosion resistance on the contrary.This means easy operating and minimizing burden to waste water dis posal.The zirconium that the chemical conversion coating that forms in this step is contained and the amount of phosphorus better are respectively 1-100mg/m
2If this amount then can weaken corrosion resistance unfavourably less than 1mg.If this amount surpasses 100mg, then can weaken cohesive unfavourably.
In following step, on above-mentioned chemical conversion coating, form the erosion shield formed by resin and/or comprise water-base resin and form hydrophilic coating as the hydrophilic treated aqueous solution of key component by use.On above-mentioned chemical conversion coating, can form above-mentioned erosion shield and do not form described hydrophilic coating, perhaps can form described hydrophilic coating and do not form described erosion shield.And, can form erosion shield and hydrophilic coating.
In order to give lubricity, can on the hydrophilic coating that adopts said method to obtain, form a lubricant coating that derives from water-base resin again.
Like this, on above-mentioned chemical conversion coating, can form the hydrophilic coating (2 layers of processing) that (1) derives from water-base resin, (2) derive from the hydrophilic coating of water-base resin, on its top, form the lubricant coating (3 layers of processing) that derives from water-base resin, (3) derive from the erosion shield (2 layers of processing) of resin, (4) derive from the erosion shield of resin, on its top, form the hydrophilic coating (3 layers of processing) that derives from water-base resin, (5) derive from the hydrophilic coating (2 layers of processing) of waterglass and water-base resin, (6) derive from the hydrophilic coating of waterglass and water-base resin, on its top, form the lubricant coating (3 layers of processing) that derives from water-base resin, (7) derive from the hydrophilic coating (2 layers of processing) of colloidal silica and water-base resin or the hydrophilic coating that (8) derive from colloidal silica and water-base resin, on its top, form any in the lubricant coating (3 layers of processing) derive from water-base resin.
Used water-base resin can be the resin of using always in forming described hydrophilic coating.Have (a) that for example can address contains the polymerizable aqueous compounds of the unsaturated polymerizable of carboxyl and/or hydroxyl, (b) contain the natural polymeric compounds or derivatives thereof of carboxyl and/or hydroxyl, (c) aqueous alkide resin, (d) water-based Malaysia carburetion (maleiated oils), (e) aqueous polyester resin, (f) water-based polybutadiene, (g) aqueous polyamide resin, (h) aqueous epoxy resins, (i) waterborne polyurethane resin, (j) aqueous phenolic aldehyde resin, (k) water-compatible amino resin and their mixture.When needed, crosslinking agent and these resin-bonded can be got up use.
As day disclosure communique flat-disclose among the 7-102189, equally better be with in the above-mentioned water-base resin (a)-(k) at least a with comprise the polymerizable aqueous compounds that is not less than 10 weight % (is benchmark in the solid) polyoxyalkylene chain and combine use.
Comprise poly-(methyl) acrylic acid, (methyl) acrylic acid-(methyl) acrylate copolymer, styrene-(methyl) acrylate copolymer, vinylite polyvinyl alcohol, PVP, (methyl) acrylamide derivative polymer such as N-methylol (methyl) acrylamide etc. as the example of the polymerizable aqueous compounds (a) of the described unsaturated polymerizable that contains carboxyl and/or hydroxyl through partly-hydrolysed acquisition.
As the natural polymeric compounds or derivatives thereof (b) that contains carboxyl and/or hydroxyl, that can address for example has cellulose derivative such as carboxymethyl cellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropyl cellulose (HPC), methylcellulose (MC), ethyl cellulose (EC), ethylhydroxyethylcellulose (EHEC) etc., methylcellulose derivative and its sodium, potassium and an ammonium salt etc.
As aqueous alkide resin (c), the compound that has polyalcohol such as glycerine, pentaerythrite, ethylene glycol, trimethylolethane etc. and the higher fatty acids that derives from oil such as binary acid such as palmitic acid, phthalic anhydride, maleic anhydride etc. to obtain that can address through dehydrating condensation.
As aqueous polyester resin (e), that can address has a hydroxyl and 1 with mylar, 2, the 4-benzenetricarboxylic anhydride is through the half ester reaction, with in the amine and remaining carboxyl and product carried out the compound of hydrophilically modified acquisition and with polyethylene glycol and polyacid reacts and the compound that the mylar of gained carried out hydrophilically modified acquisition.
As water-based polybutadiene (f), the monomer that having of can addressing contains hydrophilic group and the copolymer of butadiene.As aqueous polyamide resin (g), the polyamide that the polycondensation from the ring-opening polymerisation of epsilon-caprolactams or hexamethylene diamine and adipic acid is obtained that has that can address carries out the resin that solubilising obtains.
As aqueous epoxy resins (h), that can address has aqueous epoxy resins such as aliphatic polyol two or polyglycidyl ether, dicarboxylic acids diglycidyl ether, nitrogenous epoxide that contains heterocycle etc., be added to emulsifying agent in the water or be added to water and the mixed solution of organic solvent in, dispersed/emulsified epoxy resin or modified epoxy wherein, thereby the water-dispersed epoxy resin that the resin in dissolving or the dispersed/emulsified water obtains.
As waterborne polyurethane resin (i), having for solubilising of can addressing introduced anion or cation group and the compound that obtains in molecule.The terminal isocyanate group (isocyanato group) that bisulfites is added to polyurethane prepolymer that has that also can address is gone up the resin that the resin solubilising is obtained with sealing isocyanate group and the hydrophily by sulfonate.The useful end-capping reagent sealing polyurethane prepolymer that also can address, the then resin that firmly its emulsification/dispersion is obtained.
As aqueous phenolic aldehyde resin (j), compound that having of can addressing contains phenol type hydroxyl such as phenol, xylenols, to the polycondensation product with aldehyde such as formaldehyde, furfural etc. such as alkylphenol, p-phenyl phenol, chlorophenol, bisphenol-A, phenolsulfonic acid, resorcinol.Usually known have phenolic resins, cresol-formaldehyde resin, phenol-furfural resin, a resorcinol resin etc.
As water-compatible amino resin (k), the melamine resin that melamine resin such as normal-butylization are arranged that can address, the melamine resin of isobutyl etc., and carbamide resin, it is water-soluble that all these resins all make it have.
As the described polymerizable aqueous compounds that is not less than 10 weight % (is benchmark in the solid) polyoxyalkylene chain that comprises, that can address has PEO (PEO), PEP-101, oxirane-methylene oxygen (methylene oxide) copolymer etc.
Although the concentrated aqueous solution of dilute with water uses the above-mentioned hydrophilic treated aqueous solution usually, the concentration of the water-base resin after the dilution is preferably 1-50 weight %, more preferably 2-20 weight %.
Above-mentioned crosslinking agent can be a water cross-linking agent, and it is a kind of metallic compound that can form complex with various described water-base resins.As an example, the compound that oxide, oxide salt, halide, nitrate, sulfate, dihydric phosphate or hydrophosphate, silicate, carbonate, acylate or the complex salts etc. that comprise chromium, titanium, aluminium, zinc, zirconium are arranged that can address.
Have in the scope of adverse effect in film forming not, in being used to form the water-base resin of described hydrophilic coating, can add various additives water-base resin.That can address as an example, has lubricant, anticorrisive agent, mildewcide, antiseptic, surfactant, pigment and a dyestuff.In order to give higher hydrophily, better be to add colloidal silica or waterglass.
The painting method of above-mentioned aqueous treatment solution comprises rolling method, scraping article rubbing method, dip coating, spraying process and spread coating etc.In described painting method, when adopting rolling method, for example, can obtain hydrophilic coating applying back 10 seconds to 1 of dry coating minute under 150-270 ℃ temperature.Look the kind of used water-base resin, film forming often can not be satisfactory when at the baking temperature that is lower than 150 ℃, and when surpassing 270 ℃, owing to paint baking over has lost hydrophily.
The thickness of hydrophilic coating better is not less than 0.05g/m
2, 0.1-20g/m more preferably
2If the thickness of coating is less than 0.05g/m
2, the hydrophilic life-span of fin material and processability variation all then.
Resin as forming described erosion shield can use the resin that is usually used in giving corrosion resistance.
Also without particular limitation to the water-base resin that is used to form described lubricant coating, be water miscible those resins but can use in described water-base resin.
The aluminium radiator fin material of being made by the manufacture method of the invention described above is a kind of like this aluminium radiator fin material, is formed with chemical conversion coating thereon, is formed with erosion shield and/or hydrophilic coating on the top of described conversion coating.The zirconium that chemical conversion coating is contained and the amount of phosphorus better are respectively 1-100mg/m
2
Manufacture method by aluminium radiator fin material of the present invention comprises that using the aluminum ions Treatment Solution that comprises particular range to carry out chemical conversion handles, and applies hydrophily more thereon and handles.Because above-mentioned aluminium ion forms the chemical conversion coating of toughness with effective fluorine ion, when on this chemical conversion coating, forming erosion shield and/or hydrophilic coating, just can make and have weatherability, moisture resistivity and the fusible fin material that the fin material of handling with conventional chromate is equal to or also will be good.
Because the aluminium radiator fin material of the present invention that makes through above-mentioned manufacture method has good weatherability, moisture resistivity and cohesive, so it can be widely used as the fin material of heat exchanger such as air-conditioner etc.
Embodiment
Following embodiment and Comparative Examples are used for further describing the present invention.
Embodiment 1
Preparation chemical conversion Treatment Solution, its method are to add fluorine zirconic acid, phosphoric acid and hydrofluoric acid, and its amount is corresponding for each listed ion concentration of each ion that makes gained and table 1, adds the 500ppm tannic acid subsequently, with ammoniacal liquor the pH value is adjusted to 2.Use Kyoto Koken ' s ICP to measure Zr, phosphoric acid and Al ion; Measure effective fluorine ion with fluorine ionometer; Use Shimadzu Corporation ' s TOC to set up calibration curve and measure tannic acid.
Then, (JIS-A1100) is cut into 200 * 250mm with the aluminium radiator fin material, the preparation test piece.With concentration is that the degreasing agent (Surf Cleaner 340, the product of Nippon Paint Co.) of 1 weight % sprays 5 seconds of these test pieces in the time of 70 ℃, washes with water then.Using above-mentioned chemical conversion Treatment Solution, is that 55 ℃ and injecting time are one by one continuous chemical conversion to be carried out in test piece under the condition in 5 seconds to handle in the temperature of Treatment Solution.In continuous chemical conversion processing procedure, the composition concentration of Treatment Solution is little by little diluted.Therefore, in order to keep each component concentrations in the chemical conversion Treatment Solution, monitor solution by composition analysis, and adjust with concentrated solution.Like this, the aluminium ion that elutes from test piece accumulates in the chemical conversion Treatment Solution gradually, and finally to reach concentration be 1,000ppm.In order further to improve aluminium ion concentration, aluminum nitrate is dissolved in the solution, obtaining (aluminium ion concentration) is 2, the composition solution of 000ppm.
To being 50,200,1 with above-mentioned initial composition solution with corresponding to aluminium ion concentration, 000 and 2, organic/inorganic complexes hydrophilic modifier (Surf Alcoat131 is used in the test piece that the solution-treated of 000ppm is crossed respectively, Nippon Paint Co.) carrying out hydrophily handles, make the aluminium radiator fin material, adopt following method that it is carried out corrosion resistance and moisture resistivity evaluation then.As a result, when being not less than 200ppm, aluminium ion concentration obtained all gratifying result on corrosion resistance and moisture resistivity.The results are shown in Table 1.
＜corrosion resistance 〉
Salting liquid jet test: in the time of 35 ℃, spray test piece, estimate the degree that forms white rust after 500 hours with 5%NaCl solution.
◎: do not get rusty
Zero: get rusty slightly
△: medium getting rusty
*: obviously get rusty
All get rusty in all places of * *:
＜moisture resistivity 〉
Be not less than 50 ℃ and relative humidity under 98% the environment and carry out moisture resistivity test 500 hours, estimate the rusting rate of test piece.
◎: not decolouring
Zero: decolouring slightly
△: medium decolouring
*: obviously decolouring
All decolour in all places of * *:
Table 1
Can also estimate the cohesive of above-mentioned aluminium radiator fin material by following mode.The results are shown in Table 2.＜cohesive〉test piece was immersed in the mobile water 250 hours, carry out disbonded test through wiping.Zero: do not have unusual △: peel off slightly *: peel off
| The trend of aluminium ion concentration (ppm) | |||||
| ??????0 | ????50 | ???200 | ???1000 | ???2000 | |
| The Zr ion | ????300ppm | ??300ppm | ??300ppm | ??300ppm | ??300ppm |
| Phosphate anion | ????300ppm | ??300ppm | ??300ppm | ??300ppm | ??300ppm |
| The Al ion | ????0ppm | ??50ppm | ??200ppm | ??1000ppm | ??2000ppm |
| Effective F ion | ????5ppm | ??5ppm | ??5ppm | ??5ppm | ??5ppm |
| The pH value | ????2 | ????2 | ????2 | ????2 | ????2 |
| Tannic acid | ??500ppm | ??500ppm | ??500ppm | ??500ppm | ??500ppm |
| Corrosion resistance | ????△ | ????△ | ????○ | ????◎ | ????◎ |
| Moisture resistivity | ????△ | ????△ | ????◎ | ????◎ | ????◎ |
And, be 1 from aluminium ion concentration, on the chemical conversion coating of the aluminium radiator fin material that the test piece that 000ppm handled is made, adopt fluorescent X-ray analysis to measure the (mg/m of weight separately of zirconium or phosphorus with fluorescent X-ray analysis instrument 3070 (making) by Rigaku-sha
2).The results are shown in Table 4.
Embodiment 2-18, Comparative Examples 1-10 and reference example
Press embodiment 1 identical step and make fin material, different is the kind that changes each ion concentration, tannic acid concentration, pH value, sprayed solution temperature, injecting time, chemical conversion water cleaning afterwards or omit this step and hydrophilic treated solution, estimates their corrosion resistance, moisture resistivity and cohesive.Regulate aluminium ion concentration by adding aluminum nitrate.For reference example, adopt conventional phosphate-chromate to handle and form chemical conversion coating.The results are shown in table 2 and 3.
In Comparative Examples 1,2 and 8, measure (the mg/m of weight separately of zirconium in the chemical conversion coating of aluminium radiator fin material or phosphorus by embodiment 1 identical mode
2).The results are shown in Table 4.
Table 2
| Ion concentration (ppm) | The pH value | Organic acid (ppm) | The chemical conversion condition | After chemical conversion, wash with water | Hydrophilic modifier | Result of the test | ||||||||
| ????Zr | ????PO 4 | ????Al | Effective F | Temperature | Time | Corrosion resistance | Moisture resistivity | Cohesive | ||||||
| Embodiment | ??1 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ |
| ??2 | ??100 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??3 | ??1000 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??4 | ??300 | ??100 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??5 | ??300 | ??1000 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??6 | ??300 | ??300 | ??500 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??7 | ??300 | ??300 | ??2000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??8 | ??300 | ??300 | ??1000 | ????2 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??9 | ??300 | ??300 | ??1000 | ????5 | ????2.5 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??10 | ??300 | ??300 | ??1000 | ????1.5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??11 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????250 | ?55℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??12 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?45℃ | 5 seconds | Do not have | ????A | ??○ | ??◎ | ??○ | |
| ??13 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?65℃ | 5 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??14 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 3 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??15 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 10 seconds | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??16 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds dippings | Do not have | ????A | ??◎ | ??◎ | ??○ | |
| ??17 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Have | ????A | ??○ | ??○ | ??○ | |
| ??18 | ??300 | ??300 | ??1000 | ????5 | ????2 | ????500 | ?55℃ | 5 seconds | Do not have | ????B | ??◎ | ??◎ | ??○ | |
Table 3
| Ion concentration (ppm) | The pH value | Organic acid (ppm) | The chemical conversion condition | After chemical conversion, wash with water | Hydrophilic modifier | Result of the test | ||||||||
| ??Zr | ??PO 4 | ???Al | Effective F | Temperature | Time | Corrosion resistance | Moisture resistivity | Cohesive | ||||||
| Comparative Examples | ??1 | ??5 | ??300 | ??1000 | ??5 | ??2 | ????500 | ??55℃ | 5 seconds | Do not have | ????A | ?×× | ?×× | ??○ |
| ??2 | ??300 | ??5 | ??1000 | ??5 | ??2 | ????500 | ??55℃ | 5 seconds | Do not have | ????A | ??△ | ??× | ??△ | |
| ??3 | ??300 | ??300 | ??10 | ??5 | ??2 | ????500 | ??55℃ | 5 seconds | Do not have | ????A | ??△ | ??△ | ??○ | |
| ??4 | ??300 | ??100 | ??20000 | ??5 | ??2 | ????500 | ??55℃ | 5 seconds | Do not have | ????A | ?×× | ?×× | ??△ | |
| ??5 | ??300 | ??1000 | ??1000 | ??500 | ??5 | ????500 | ??55℃ | 5 seconds | Do not have | ????A | ?×× | ?×× | ??△ | |
| ??6 | ??300 | ??300 | ??1000 | ??0.1 | ??2 | ????500 | ??55℃ | 5 seconds | Do not have | ????A | ??× | ??△ | ??○ | |
| ??7 | ??300 | ??300 | ??1000 | ??5 | ??2 | ????500 | ??25℃ | 5 seconds | Do not have | ????A | ??× | ??× | ??△ | |
| ??8 | ??300 | ??300 | ??1000 | ??5 | ??2 | ????500 | ??55℃ | 0.5 second | Do not have | ????A | ?×× | ?×× | ??○ | |
| ??9 | ??300 | ??300 | ??1000 | ??5 | ??2 | ????500 | ??55℃ | 5 seconds | Do not have | Do not have | ??△ | ??△ | ??- | |
| ??10 | ??300 | ??300 | ??1000 | ??5 | ??2 | ????0 | ??55℃ | 5 seconds | Do not have | ????A | ??△ | ??○ | ??○ | |
| Reference example | Phosphate-chromating | ??55℃ | 5 seconds | Do not have | ????A | ??△ | ??△ | ??○ | ||||||
Zr ion ... .. is provided by the fluorine zirconic acid
PO
4Ion ... .. is provided by phosphoric acid
Al ion ... .. is provided by aluminum nitrate
Effective fluorine ion ... .. is provided by hydrofluoric acid
PH value ... .. regulates with ammoniacal liquor
Organic acid ... .. tannic acid
Hydrophilic modifier:
A..... organic/inorganic complexes system (Surf Alcoat 131, the product of Nippon Paint Co.)
B..... organic system (Surf Alcoat 240, the product of Nippon Paint Co.)
Phosphate-chromate is handled ... .. mixes the aqueous solution that obtains with 3.0 weight %Alsurf 407 (product of Nippon Paint Co.) and 0.4 weight %Alsurf 47 (product of Nippon Paint Co.)
Table 4
| Weight (mg/m in chemical conversion coating 2) | ||
| ????Zr | ????P | |
| Embodiment 1 | ????15 | ????6 |
| Comparative Examples 1 | ????0.2 | ????3 |
| Comparative Examples 2 | ????14 | ????0.1 |
| Comparative Examples 8 | ????0.8 | ????0.5 |
The above results shows that test piece that embodiment makes all is better than handling the test piece that makes through phosphate-chromate in the reference example on corrosion resistance and moisture resistivity, and identical with it on cohesive and hydrophily.Therefore, obviously they can be used as fin material satisfactorily.
Claims (5)
1. the manufacture method of an aluminium radiator fin material, it is included in the chemical conversion treatment step of aluminium base, forms chemical conversion coating, the hydrophilic coating that on this chemical conversion coating, forms erosion shield and/or form by water-base resin,
Described chemical conversion coating is that the composition with the chemical conversion Treatment Solution remains in the following ranges and is in that to make solution temperature be that 30-70 ℃ and processing time are to obtain under the 1-10 condition of second:
Zirconium ion 10-10,000ppm
Phosphate anion 10-10,000ppm
Aluminium ion 100-10,000ppm
Effective fluorine ion 1-500ppm
The organic acid 10-10 that in molecule, contains at least one phenol type hydroxyl, 000ppm
PH value 1.0-4.0.
2. the manufacture method of aluminium radiator fin material as claimed in claim 1, the wherein said organic acid that contains at least one phenol type hydroxyl in molecule comprises at least a material that is selected from phenol, phenolsulfonic acid, tannic acid and its derivative.
3. as the manufacture method of each described aluminium radiator fin material in the claim 1 to 2, wherein after forming described chemical conversion coating, do not wash and with the roll-in branch that anhydrates, the hydrophilic coating that forms erosion shield subsequently and/or form by water-base resin.
4. aluminium radiator fin material, it is made by each described method in the claim 1 to 3.
5. aluminium radiator fin material as claimed in claim 4, the zirconium that the chemical conversion coating of wherein said aluminium radiator fin material is contained and the amount of phosphorus are respectively 1-100mg/m
2
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000346485A JP2002146549A (en) | 2000-11-14 | 2000-11-14 | Method for producing fin material made of aluminum and fin material made of aluminum produced by the method |
| JP346485/00 | 2000-11-14 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1353296A true CN1353296A (en) | 2002-06-12 |
| CN100392341C CN100392341C (en) | 2008-06-04 |
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|---|---|---|---|
| CNB011374594A Expired - Fee Related CN100392341C (en) | 2000-11-14 | 2001-11-14 | Method of manufacturing aluminium radiator fin material and aluminium radiator fin made by said method |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2002146549A (en) |
| KR (1) | KR20020037710A (en) |
| CN (1) | CN100392341C (en) |
| MY (1) | MY144459A (en) |
| TW (1) | TW510832B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406836C (en) * | 2005-06-27 | 2008-07-30 | 株式会社神户制钢所 | Aluminium fin material |
| CN102392238A (en) * | 2011-11-07 | 2012-03-28 | 大连三达奥克化学股份有限公司 | Normal temperature skin film forming agent of aluminum profile for building, which can replace chromizing agent |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4544450B2 (en) * | 2002-12-24 | 2010-09-15 | 日本ペイント株式会社 | Chemical conversion treatment agent and surface treatment metal |
| JP2008184690A (en) * | 2002-12-24 | 2008-08-14 | Nippon Paint Co Ltd | Pretreatment method for coating |
| JP4872182B2 (en) * | 2003-03-06 | 2012-02-08 | 日本軽金属株式会社 | Aluminum coating material and manufacturing method thereof |
| DE10314700A1 (en) | 2003-03-31 | 2004-10-14 | Behr Gmbh & Co. Kg | Method for producing surface-modified workpieces |
| JP2006111901A (en) * | 2004-10-13 | 2006-04-27 | Furukawa Sky Kk | Surface-prepared aluminum material for precoat fin |
| JP2006213978A (en) * | 2005-02-04 | 2006-08-17 | Daikin Ind Ltd | Heat exchanger, refrigerating cycle apparatus and coating material used therefor |
| JP2006326863A (en) * | 2005-05-23 | 2006-12-07 | Furukawa Sky Kk | Aluminium material for precoated fin |
| KR100822169B1 (en) * | 2006-12-28 | 2008-04-16 | 캐리어 주식회사 | Evaporator for rv air conditioner |
| JP5265892B2 (en) * | 2007-07-31 | 2013-08-14 | 株式会社神戸製鋼所 | Manufacturing method of aluminum metal material fin material, and aluminum metal material fin material manufactured by the manufacturing method |
| KR101970964B1 (en) * | 2012-08-16 | 2019-04-26 | 주식회사 두원공조 | Condenser for air conditioning apparatus of vehicle and manufacturing method of the same |
| JP6495702B2 (en) * | 2015-03-19 | 2019-04-03 | 株式会社神戸製鋼所 | Surface treatment method and surface treatment apparatus |
| CN106435553B (en) * | 2016-12-16 | 2019-01-25 | 长沙艾森设备维护技术有限公司 | A kind of zirconium-based metallic surface treating agent and application |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5315687B2 (en) * | 1973-10-04 | 1978-05-26 | ||
| JP3051196B2 (en) * | 1991-04-17 | 2000-06-12 | 大日本塗料株式会社 | Coated aluminum material and method for producing the same |
| CA2123034C (en) * | 1993-05-07 | 2000-10-17 | Katsuyoshi Yamasoe | Hydrophilic surface treating aqueous solution, hydrophilic surface treating method and hydrophilic surface treating film |
| US5380374A (en) * | 1993-10-15 | 1995-01-10 | Circle-Prosco, Inc. | Conversion coatings for metal surfaces |
-
2000
- 2000-11-14 JP JP2000346485A patent/JP2002146549A/en active Pending
-
2001
- 2001-11-07 MY MYPI20015132A patent/MY144459A/en unknown
- 2001-11-14 KR KR1020010070821A patent/KR20020037710A/en not_active Application Discontinuation
- 2001-11-14 CN CNB011374594A patent/CN100392341C/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100406836C (en) * | 2005-06-27 | 2008-07-30 | 株式会社神户制钢所 | Aluminium fin material |
| CN102392238A (en) * | 2011-11-07 | 2012-03-28 | 大连三达奥克化学股份有限公司 | Normal temperature skin film forming agent of aluminum profile for building, which can replace chromizing agent |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020037710A (en) | 2002-05-22 |
| CN100392341C (en) | 2008-06-04 |
| JP2002146549A (en) | 2002-05-22 |
| TW510832B (en) | 2002-11-21 |
| MY144459A (en) | 2011-09-30 |
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Address after: Osaka Japan Patentee after: NIPPON PAINT HOLDINGS CO.,LTD. Patentee after: Kobe Steel, Ltd. Address before: Osaka Japan Patentee before: NIPPON PAINT Co.,Ltd. Patentee before: Kobe Steel, Ltd. |
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Effective date of registration: 20160118 Address after: Tokyo, Japan Patentee after: NIPPON PAINT SURF CHEMICALS CO.,LTD. Patentee after: Kobe Steel, Ltd. Address before: Osaka Japan Patentee before: NIPPON PAINT HOLDINGS CO.,LTD. Patentee before: Kobe Steel, Ltd. |
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Granted publication date: 20080604 Termination date: 20191114 |