WO2011065482A1 - アルミニウム材製熱交換器の耐食処理方法 - Google Patents
アルミニウム材製熱交換器の耐食処理方法 Download PDFInfo
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- WO2011065482A1 WO2011065482A1 PCT/JP2010/071129 JP2010071129W WO2011065482A1 WO 2011065482 A1 WO2011065482 A1 WO 2011065482A1 JP 2010071129 W JP2010071129 W JP 2010071129W WO 2011065482 A1 WO2011065482 A1 WO 2011065482A1
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- heat exchanger
- treatment
- hydrophilic
- aluminum
- corrosion resistance
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Classifications
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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
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
- B23K1/0012—Brazing heat exchangers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/20—Preliminary treatment of work or areas to be soldered, e.g. in respect of a galvanic coating
- B23K1/203—Fluxing, i.e. applying flux onto surfaces
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
-
- 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
- C23C22/83—Chemical 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
- 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
- F28F19/04—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of rubber; of plastics material; of varnish
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
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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
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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
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2275/00—Fastening; Joining
- F28F2275/04—Fastening; Joining by brazing
Definitions
- the present invention relates to an aluminum heat exchanger (hereinafter also referred to as an NB heat exchanger) that has been flux brazed by a Nocolok brazing method (hereinafter also referred to as an NB method), particularly an automotive air conditioner. More particularly, the surface of the heat exchanger made of aluminum material is treated with a hydrophilic treatment liquid containing lithium ions without subjecting the heat exchanger to chemical conversion treatment.
- the present invention relates to a corrosion treatment method for an NB heat exchanger that can greatly improve the corrosion resistance without impairing the heat resistance and can also improve the deodorization property.
- aluminum and its alloys constituting aluminum fins and aluminum tubes are usually excellent in rust prevention, but if condensed water stays on the fin surface for a long time, Oxygen concentration cells are formed, or pollutants in the atmosphere are gradually adhered and concentrated to promote hydration and corrosion reactions. This corrosion product accumulates on the fin surface, impairs heat exchange characteristics, and becomes white fine powder and is discharged by a blower.
- an aluminum heat exchanger is washed with acid, then immersed in a zirconium-based chemical conversion treatment solution, and then subjected to zirconium chemical conversion treatment, and then modified polyvinyl alcohol, phosphorus compound salt, boron compound
- a surface treatment method for imparting good hydrophilicity and deodorization to the aluminum surface by immersing it in a hydrophilic treatment solution mixed with a salt, a hydrophilic organic compound, a crosslinking agent, etc. (patent) Reference 1).
- an aluminum heat exchanger used in an air conditioner for automobiles is a structure in which many aluminum fins and aluminum tubes are assembled, and then aluminum fins or aluminum fins and aluminum tubes are joined together. Since a strong and dense oxide film is formed, joining by brazing or soldering other than the mechanical joining method cannot be easily performed.
- the VB method vacuum
- Brazing method was mainly performed.
- halogen-based fluxes have been developed as a means for effectively removing and destroying oxide films. Brazing is easy to manage, the furnace is inexpensive, and brazing costs are low.
- a flux brazing method represented by the NB method for brazing has come to be used.
- This NB method is a method of assembling aluminum fins and the like and then brazing the aluminum fins and the like in nitrogen gas using a flux such as KAlF 4 and K 2 AlF 5 . It has also been applied to fabrication.
- the NB heat exchanger manufactured by this NB method has a non-uniform surface condition because flux unavoidably remains on the aluminum surface, and uniform surface treatment such as chemical conversion treatment and hydrophilization treatment cannot be performed. There is a problem peculiar to NB heat exchangers such as insufficient corrosion resistance and adhesion.
- the NB heat exchanger is immersed in a zirconium-based chemical conversion treatment solution and then subjected to zirconium chemical conversion treatment, and then modified with polyvinyl alcohol or polyoxyalkylene.
- a surface treatment method has been proposed in which a hydrophilic treatment is performed by immersing in a hydrophilic treatment liquid in which polyvinyl alcohol, an inorganic crosslinking agent, a guanidine compound, etc. are mixed to provide a deodorizing effect in addition to a good corrosion resistance and hydrophilic effect. (See Patent Document 2).
- a heat exchanger for forming a film having a dry film thickness of 0.2 to 5 ⁇ m is disclosed by coating and baking the hydrophilic treatment agent on the surface of the aluminum fin material.
- a method for hydrophilizing an aluminum fin material is disclosed (see Patent Document 3).
- the hydrophilic treatment agent for heat exchanger fins described in Patent Document 3 contains polyvinyl alcohol and a specific acrylic resin, and preferably contains lithium silicate. This technique is intended to prevent frost formation by improving hydrophilicity by reducing the water contact angle of the resulting film.
- the hydrophilization treatment agent disclosed in Citation 3 is for the heat exchange fin material of the outdoor unit, and the hydrophilization treatment agent is applied to the aluminum plate before assembling the aluminum fins. Yes, the above-mentioned problem peculiar to the hydrophilic treatment for the heat exchanger manufactured by the NB method does not exist.
- the present invention has been made under such circumstances, and a chemical conversion treatment is performed in advance on an aluminum material heat exchanger flux-brazed by the NB method, particularly an aluminum material heat exchanger used in an air conditioner for automobiles.
- An object of the present invention is to provide a corrosion-resistant treatment method for a heat exchanger that can significantly improve the corrosion resistance without impairing the hydrophilicity and can also improve the deodorization performance.
- the present inventors have surfaced a heat exchanger made of aluminum material flux-brazed by a NB method with a hydrophilic treatment liquid containing a hydrophilic resin and lithium ions. It has been found that the treatment can significantly improve the corrosion resistance and also improve the deodorizing property without impairing the hydrophilicity of the surface. This is considered to be due to the following actions. Lithium ions are considered to have an effect of suppressing the corrosion starting point by acting on the flux dissolved under the surface treatment (hydrophilic treatment, chemical conversion treatment) film in the corrosive environment and making it slightly soluble as Li 2 AlF 5 or the like. . That is, the present invention improves the corrosion resistance of an aluminum material heat exchanger by acting on the flux remaining on the aluminum material. The present invention has been completed based on such findings.
- a hydrophilization treatment liquid is attached to an aluminum heat exchanger that has been flux brazed by the Nocolok brazing method, followed by baking treatment to form a hydrophilic coating on the surface of the aluminum heat exchanger.
- an aluminum material heat exchanger flux-brazed by the NB method is subjected to a surface treatment with a hydrophilic treatment liquid containing lithium ions.
- a corrosion-resistant treatment method for heat exchangers that can significantly improve corrosion resistance without sacrificing surface hydrophilicity, improve deodorization, and maintain long-term corrosion resistance and hydrophilicity. can do.
- the chemical conversion treatment performed before the hydrophilization treatment can be omitted, the number of steps can be reduced, thereby reducing waste water and realizing a compact processing apparatus.
- the corrosion resistance treatment method for an aluminum material heat exchanger according to the present invention is such that an aluminum material heat exchanger flux-brazed by the NB method is brought into contact with a hydrophilic treatment liquid and then baked to render a hydrophilic coating on the surface.
- the hydrophilic treatment liquid contains a hydrophilic resin and lithium ions, and the lithium concentration in the hydrophilic film is 0.05 to 25% by mass.
- the heat exchanger used in the present invention acts on the flux remaining on the surface of the NB heat exchanger to greatly improve the corrosion resistance of the heat exchanger. Therefore, the heat exchanger used in the present invention is an aluminum material heat exchanger flux-brazed by the NB method. The flux inevitably remains on the surface of the heat exchanger.
- the NB heat exchanger include an aluminum material heat exchanger used for an air conditioner of an automobile.
- the “aluminum material” refers to aluminum or an aluminum alloy.
- fins and tubes made of aluminum are joined by a known NB method in which brazing is performed in nitrogen gas.
- the flux used in the NB method is not particularly limited as long as the flux includes a salt composed of lithium ions and an anion that forms a hardly soluble salt, and a normal halogen-based flux used in the NB method can be used.
- a normal halogen-based flux used in the NB method can be used.
- the halogen-based flux include KAlF 4 , K 2 AlF 5 , K 3 AlF 6 , CsAlF 4 , Cs 3 AlF 6 and Cs 2 AlF 5 , and a mixture of two or more of these.
- the hydrophilization treatment liquid used in the present invention is an aqueous solution or aqueous dispersion containing a hydrophilic resin and lithium ions in an aqueous solvent.
- the hydrophilic resin is not particularly limited, but is preferably a water-soluble or water-dispersible hydrophilic resin having a hydroxyl group, a carboxyl group, an amide group, an amino group, a sulfonic acid group and / or an ether group in the molecule.
- the hydrophilic resin preferably forms a film having a contact angle with water droplets of 40 degrees or less. Since such a film exhibits good hydrophilicity, sufficient hydrophilicity can be imparted to an object to be processed by applying a hydrophilic treatment liquid containing the hydrophilic resin.
- hydrophilic resin examples include polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide, carboxymethyl cellulose, chitosan, polyethylene oxide, water-soluble nylon, and a copolymer of monomers forming these polymers.
- An acrylic polymer having a polyoxyethylene chain such as 2-methoxypolyethylene glycol methacrylate / 2-hydroxylethyl acrylate copolymer is preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.
- hydrophilic resins have excellent hydrophilicity and water resistance, have no odor of themselves, and are difficult to adsorb odorous substances. Therefore, the hydrophilic treatment liquid containing the hydrophilic resin is hydrophilic and deodorizing. Since it is highly resistant and the resulting hydrophilized film is not easily deteriorated even when exposed to water droplets or flowing water, it is optionally contained and contains inorganic substances such as silica and other residual monomers that emit their own dusty odors and unpleasant odors of adsorbents. Since the component is difficult to be exposed, it is possible to prevent the processing agent itself from being scattered and generating a dusty odor.
- the hydrophilic resin preferably has a number average molecular weight in the range of 1,000 to 1,000,000.
- the number average molecular weight is 1000 or more, the film-forming property, hydrophilicity and other film properties are good.
- the number-average molecular weight is 1 million or less, the viscosity of the hydrophilized liquid does not become too high and the workability is improved. And film properties are improved.
- a more preferred number average molecular weight is in the range of 10,000 to 200,000.
- the number average molecular weight of hydrophilic resin is the value of standard polystyrene conversion measured by the gel permeation chromatography method (GPC method).
- the hydrophilic resin is more preferably polyvinyl alcohol because it is excellent in terms of preventing odor and imparting hydrophilicity, and in particular, polyvinyl alcohol and / or modified polyvinyl alcohol having a saponification degree of 90% or more. Particularly preferred.
- (A) Polyvinyl alcohol having a saponification degree of 90% or more Polyvinyl alcohol having a saponification degree of 90% or more originally has hydrophilicity-imparting performance, but is a hydrophilic resin with high water resistance, and can be densely coated with aluminum fins. Moreover, since the water resistance of resin is high, the deodorizing property and the adhesion odor suppression effect are high.
- the saponification degree is particularly preferably 95% or more from the viewpoint of the above effects. If the saponification degree is less than 90%, the hydrophilicity may be inferior.
- the content thereof is 10% relative to the total solid content of the hydrophilic treatment liquid from the viewpoint of the above effect. It is preferably ⁇ 90% by mass, and more preferably 20 ⁇ 80% by mass.
- n represents an integer of 1 to 500
- R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
- R 2 represents a hydrogen atom or a methyl group.
- Polyoxyalkylene-modified polyvinyl alcohol which is a polyoxyalkylene ether group represented by the formula:
- the polyoxyalkylene-modified group is preferably 0.1 to 5% of the pendant group, and the polymerization degree n of the polyoxyalkylene group is preferably 3 to 30.
- the polyoxyalkylene-modified polyvinyl alcohol plays a particularly role of imparting hydrophilicity in the hydrophilization solution because of the hydrophilicity of the polyoxyalkylene group.
- the content thereof is from 3 to 60 with respect to the total solid content of the hydrophilization treatment liquid from the viewpoint of imparting hydrophilicity.
- the mass is preferably 3% by mass, more preferably 3 to 40% by mass, and even more preferably 5 to 30% by mass.
- the polyvinyl alcohol having a saponification degree of 90% or more and the polyoxyalkylene-modified polyvinyl alcohol are used in combination as the hydrophilic resin, from the viewpoint of the balance between hydrophilicity and odor, from the viewpoint of the balance between hydrophilicity and odor,
- the blending ratio is preferably in the range of 10: 1 to 1: 4, more preferably in the range of 5: 1 to 1: 3 by mass ratio.
- the hydrophilic treatment solution contains lithium ions together with the hydrophilic resin described above.
- the lithium ion source is not particularly limited as long as it is a lithium compound capable of forming lithium ions in the hydrophilization treatment solution.
- lithium hydroxide, lithium sulfate, lithium carbonate, lithium nitrate, lithium acetate, citric acid Lithium, lithium lactate, lithium phosphate, lithium oxalate, lithium silicate, lithium metasilicate, or the like can be used.
- lithium hydroxide, lithium sulfate, and lithium carbonate are preferably used because they have little influence on odor.
- a lithium ion source may be used individually by 1 type, and may be used in combination of 2 or more type.
- the hydrophilization treatment liquid containing lithium ions in this way, the aluminum material heat exchanger flux-brazed by the NB method is surface-treated to form a hydrophilized film, thereby improving the corrosion resistance. It can be greatly improved.
- the flux residue is mainly a composite compound of potassium fluoride or cesium fluoride and aluminum fluoride, and the present invention is obtained by performing surface treatment with the hydrophilization treatment solution containing lithium ions, and the like with potassium ions in the flux residue.
- a layer containing a hardly soluble lithium salt is formed at least at the interface between the flux residue and the hydrophilized film, thereby improving the rust prevention (corrosion resistance) of the flux residue.
- the present invention acts on the flux residue to improve the corrosion resistance. Further, since the lithium in the hydrophilized film remains for a long time, the above effect can be maintained for a long time.
- the lithium concentration (concentration in the total solid content) in the hydrophilized film is 0.05 to 25% by mass, preferably 0, from the viewpoint of improving the corrosion resistance and balancing the economy. 1 to 10% by mass.
- the lithium concentration (concentration in the total solid content) in the hydrophilic coating is less than 0.05% by mass, the corrosion resistance is insufficient, and even if it exceeds 25% by mass, the corrosion resistance is not improved, and the economic efficiency is improved. bad.
- the hydrophilic treatment liquid may contain a crosslinking agent as necessary for the purpose of improving the water resistance of the hydrophilic coating formed using the hydrophilic treatment liquid.
- a crosslinking agent an inorganic crosslinking agent or an organic crosslinking agent that reacts with a hydroxyl group of polyvinyl alcohol or modified polyvinyl alcohol can be used.
- the inorganic crosslinking agent include silica compounds such as silicon dioxide, zirconium compounds such as zircon ammonium fluoride and zircon ammonium carbonate, metal chelate compounds such as titanium chelate, phosphates such as Ca, Al, Mg, Fe and Zn, and condensed phosphorus. Examples thereof include phosphorus compounds such as acids.
- examples of the organic crosslinking agent include melamine resin, phenol resin, epoxy compound, blocked isocyanate compound, oxazoline compound, carbodiimide compound and the like. These crosslinking agents may be used individually by 1 type, and may be used in combination of 2 or more types.
- the content of the crosslinking agent is preferably 0.1 to 70% by mass with respect to the total solid content of the hydrophilization treatment liquid, from the viewpoint of the balance between the crosslinking effect and economic efficiency. More preferably, it is 2 to 50% by mass.
- the hydrophilic treatment liquid may contain a guanidine compound and / or a salt thereof as necessary.
- This guanidine compound has the following general formula (3)
- Y represents —C ( ⁇ NH) — (CH 2 ) m —, —C ( ⁇ O) —NH— (CH 2 ) m —, or —C ( ⁇ S) —NH— (CH 2 ) M represents.
- m represents an integer of 0 to 20.
- n represents a positive integer.
- k represents 0 or 1.
- X represents hydrogen, an amino group, a hydroxyl group, a methyl group, a phenyl group, a chlorophenyl group, or a methylphenyl group (tolyl group).
- Z is hydrogen, amino group, hydroxyl group, methyl group, phenyl group, chlorophenyl group, methylphenyl group (tolyl group), or the following general formula (4);
- guanidine compound is not particularly limited.
- guanidine aminoguanidine, guanylthiourea, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, 1-o-tolylbiguanide, polyhexamethylenebiguanidine.
- polyhexaethylene biguanidine, polypentamethylene biguanidine, polypentaethylene biguanidine, polyvinyl biguanidine, polyallyl biguanidine, and the like One of these guanidine compounds may be used alone, or two or more thereof may be used in combination.
- examples of the salt of the guanidine compound include inorganic acid salts such as phosphate, hydrochloride and sulfate, and organic acid salts such as acetate and gluconate. These salts may be used individually by 1 type, and may be used in combination of 2 or more types.
- one or more guanidine compounds may be used, one or more guanidine compound salts may be used, or one or more guanidine compounds and one or more guanidine compound salts may be used in combination.
- This guanidine compound or a salt thereof has an effect of imparting excellent rust prevention properties to a hydrophilic film formed using the hydrophilic treatment liquid.
- the guanidine compound preferably has a mass average molecular weight in the range of a lower limit of 59 and an upper limit of 1,000,000. Since the molecular weight of guanidine that minimizes the molecular weight in the general formula (3) is 59, it cannot be less than 59, and if it exceeds 1 million, it may not be water-soluble.
- the lower limit is more preferably 300, and even more preferably 500.
- the upper limit is more preferably 100,000 and more preferably 20,000.
- the mass average molecular weight of the guanidine compound salt is the sum of the mass average molecular weight of the guanidine compound and the total molecular weight of the salt added to the guanidine compound.
- the mass mean molecular weight of the said guanidine compound is the value of standard polystyrene conversion measured by GPC method.
- the guanidine compound having a biguanide structure and / or a salt thereof is not particularly limited, and examples thereof include polyhexamethylene biguanidine, 1-o-tolyl biguanide, chlorhexiridine gluconate, and / or a salt thereof. Can do.
- the said guanidine compound and / or its salt may be used independently, and may use 2 or more types together.
- the guanidine compound and / or salt thereof has an excellent antirust effect, and its content in the hydrophilization treatment liquid is determined from the viewpoint of balance between the antirust effect and economy, and the like.
- the total solid content is preferably 1 to 20% by mass, more preferably 2 to 10% by mass.
- a dispersant in the hydrophilization treatment liquid, as other optional components, a dispersant, a rust preventive additive, a pigment, a silane coupling agent, an antibacterial agent (preservative), a surfactant, a lubricant, a deodorant, as necessary.
- An agent or the like can be appropriately contained. It does not specifically limit as said dispersing agent, Surfactant, a dispersion resin, etc. can be mentioned.
- the antirust additive is not particularly limited, and examples thereof include tannic acid, imidazole compound, triazine compound, triazole compound, hydrazine compound, zirconium compound and the like. Among these, a zirconium compound is preferable because rust prevention can be effectively imparted.
- the zirconium compound is not particularly limited, and examples thereof include alkali metal fluorozirconates such as K 2 ZrF 6 ; soluble fluorozirconates such as fluorozirconates such as (NH 4 ) 2 ZrF 6 ; and H 2 ZrF 6 . Fluorozirconic acid and the like; zirconium fluoride; zirconium oxide and the like.
- the pigment examples include titanium oxide (TiO 2 ), zinc oxide (ZnO), zirconium oxide (ZrO), calcium carbonate (CaCO 3 ), barium sulfate (BaSO 4 ), alumina (Al 2 O 3 ), kaolin clay, carbon Examples thereof include inorganic pigments such as black, iron oxide (Fe 2 O 3 , Fe 3 O 4 ), aluminum oxide (Al 2 O 3 ), and various colored pigments such as organic pigments.
- the inclusion of a silane coupling agent is preferred in that the affinity between the hydrophilic resin and the pigment is improved, and adhesion and the like can be improved.
- the silane coupling agent is not particularly limited. For example, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -methacryloxypropyltriethoxysilane, N -[2- (vinylbenzylamino) ethyl] -3-aminopropyltrimethoxysilane and the like can be mentioned.
- the antibacterial agent is not particularly limited, and conventionally known antibacterial agents such as 2- (4-thiazolyl) benzimidazole, zinc pyrithione, and benzisothiazoline can be used.
- the solvent for the hydrophilic treatment liquid is not particularly limited, but an aqueous solvent mainly composed of water is preferable from the viewpoint of waste liquid treatment. Further, a solvent may be used in combination in order to improve the film forming property and form a more uniform and smooth film.
- the solvent is not particularly limited as long as it is generally used for paints and can be uniformly mixed with water, and examples thereof include alcohol-based, ketone-based, ester-based and ether-based organic solvents. it can.
- the amount of the solvent used is preferably 0.01 to 5% by mass of the solvent in the hydrophilization treatment liquid.
- the hydrophilic treatment agent may adjust the pH in order to improve the stability as the treatment agent. Adjustment of pH can be performed with common acids and alkalis, such as a sulfuric acid, nitric acid, and ammonia.
- the total solid content concentration in the hydrophilization treatment liquid is preferably 1 to 11% by mass, more preferably 2 to 5% from the viewpoints of workability, uniformity and thickness of the hydrophilized film to be formed, and economic efficiency. % By mass.
- the concentration of the hydrophilic resin in the hydrophilic treatment liquid is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.
- the concentration is preferably 0.1 to 10% by mass, more preferably 0.2 to 9.0% by mass.
- polyoxyalkylene-modified polyvinyl alcohol When polyoxyalkylene-modified polyvinyl alcohol is used, its concentration is preferably 0.03 to 4.4% by mass, and more preferably 0.05 to 3.3% by mass.
- the lithium ion concentration is preferably 0.001 to 2.5% by mass, more preferably 0.05 to 1.0% by mass.
- concentration of the crosslinking agent is preferably 0.001 to 8% by mass, more preferably 0.02 to 1.0% by mass.
- concentration of the guanidine compound and / or its salt is preferably 0.01 to 5.5% by mass, more preferably 0.02 to 3% by mass.
- the total concentration of other optional components is preferably 0.001 to 5% by mass, more preferably 0.02 to 1% by mass.
- a heat exchanger made of aluminum (flux) that has been flux-brazed by the NB method is brought into contact with the above-described hydrophilization liquid and then baked to form a hydrophilized film on the surface. Rust prevention treatment is performed.
- the object to be treated is preferably subjected to a hot water washing process by a conventionally known method before the hydrophilic treatment.
- Examples of the method for adhering the hydrophilic treatment liquid to the object to be treated include an immersion method, a spray method, and a coating method.
- the immersion method is preferable. .
- the immersion treatment is usually performed at room temperature for about 10 seconds.
- the coating amount of the hydrophilic coating formed can be controlled by controlling the amount of adhesion in a wet state by air blow.
- the coating amount of the hydrophilic coating is preferably in the range of 0.1 to 5.0 g / m 2 from the viewpoint of corrosion resistance and economy.
- the coating amount is more preferably 0.1 to 1.5 g / m 2 , and still more preferably 0.2 to 1.0 g / m 2 .
- the NB heat exchanger hydrophilized with the lithium ion-containing hydrophilizing solution has a flux residue, but the surface hydrophilicity is impaired even if the heat exchanger is not subjected to chemical conversion treatment in advance. Therefore, the corrosion resistance can be greatly improved, and the deodorizing property can also be improved.
- Hydrophilization treatment may be performed with a lithium ion-containing hydrophilic treatment liquid by the method described above.
- the chemical conversion treatment method is not particularly limited, and various conventionally known chemical conversion treatments can be used.
- a chemical conversion treatment not containing Cr 6+ is preferable from the viewpoint of safety to the human body.
- Examples of such chemical conversion treatment include zirconium chemical conversion treatment and titanium chemical conversion treatment. This chemical conversion treatment is desirably performed after the hot water washing treatment of the NB heat exchanger to be processed. The following describes the zirconium chemical conversion treatment.
- Zirconium conversion treatment is a treatment of the above-mentioned object to be treated with a zirconium conversion treatment solution containing zirconium and having a pH of 3 to 5.
- the zirconium chemical conversion treatment solution containing zirconium used in the present invention is a solution in which a zirconium-based compound is dissolved in water and zirconium ions are used as active species.
- Zirconium compounds include zirconium compounds such as fluorozirconic acid and zirconium fluoride, and salts thereof such as lithium, sodium, potassium, and ammonium.
- a zirconium compound such as zirconium oxide may be dissolved with a fluoride such as hydrofluoric acid.
- the zirconium content in the zirconium chemical conversion treatment liquid is not particularly limited, but is preferably 50 to 5000 ppm, more preferably 100 to 3000 ppm, and further preferably 300 to 1500 ppm.
- the amount of the zirconium conversion coating on the aluminum material surface of the NB heat exchanger is preferably 1 to 200 mg / m 2 , more preferably 2 to 150 mg / m 2 from the viewpoint of rust prevention.
- the pH of this zirconium chemical conversion treatment solution is preferably in the range of 3-5. If the pH is 3 or more, a zirconium conversion coating can be formed without causing excessive etching with the zirconium conversion treatment solution. If the pH is 5 or less, a sufficient amount of zirconium conversion coating can be obtained without insufficient etching. Can be obtained. A more preferred pH is 3.5 to 4.5.
- the pH can be adjusted with a general acid or alkali such as sulfuric acid, nitric acid, or ammonia.
- this zirconium chemical conversion treatment liquid is used to improve rust prevention properties, such as titanium, manganese, zinc, cerium, vanadium, trivalent chromium, and other metal ions, and phenol resin.
- An agent; a silane coupling agent for improving adhesion; phosphoric acid or the like for promoting a chemical conversion reaction may be contained.
- the method of zirconium chemical conversion treatment in the present invention is not particularly limited, and any of a spray method, an immersion method, and the like may be used.
- the temperature of the zirconium chemical conversion treatment liquid is preferably 50 to 70 ° C., more preferably 55 to 65 ° C.
- the time for the zirconium chemical conversion treatment is preferably 20 to 900 seconds, more preferably 30 to 600 seconds. If it is the temperature of the process liquid of this range, and the time of a process, the zirconium chemical conversion film which has rust prevention property can be formed.
- the NB heat exchanger thus subjected to zirconium conversion treatment is surface-treated with the above-described hydrophilic treatment liquid containing lithium ions to form a hydrophilic coating with a coating amount of 0.1 to 5.0 g / m 2.
- the corrosion resistance can be significantly improved and the deodorization property can be improved as compared with the case where the chemical conversion treatment is not performed in advance without impairing the hydrophilicity of the surface.
- the corrosion resistance treatment method for an NB heat exchanger according to the present invention is a heat exchanger in which fins and tubes made of aluminum are joined and assembled by flux brazing according to the NB method as a heat exchanger that is an object to be processed.
- the present invention is applied to a heat exchanger used in an air conditioner of an automobile.
- Corrosion resistance Based on JIS Z 2371, 5 mass% salt solution was sprayed at 35 degreeC, and the white rust generation
- the corrosion resistance evaluation is preferably 8 or more. 10: No white rust generation 9: White rust generation area less than 10% 8: Less than 20% 7: Less than 30% 6: Less than 40% 5: Less than 50% 4: Less than 60% 3: 3: 70 Less than% 2: Less than 80% 1: Less than 90%
- Odor After the test heat exchanger was brought into contact with running tap water for 72 hours, the odor was smelled and evaluated based on the following evaluation criteria. The evaluation was performed by five evaluators, and an average value was calculated. The odor is preferably 2.0 or less, and more preferably 1.5 or less. 0: Odorless 1: Slightly smell 2: Smelly smell 3: Obvious smell 4: Strong smell 5: Very strong smell
- test heat exchanger As the heat exchanger, an automotive aluminum material heat exchanger (NB heat exchanger) brazed with KAlF 4 and K 3 AlF 6 fluxes was used. The flux amount of this heat exchanger was 50 mg / m 2 (fin surface) as K. About this heat exchanger, the following process I or process II was given, and the test heat exchanger was produced.
- NB heat exchanger automotive aluminum material heat exchanger
- Treatment I (Washing ⁇ Hydrophilization ⁇ Baking)
- the heat exchanger was washed with hot water at 50 ° C. for 30 seconds, and then placed in a bath of the hydrophilization treatment liquid obtained in Examples 1 to 11, 14 to 16 and Comparative Examples 1 to 2, and 4 to 5 at room temperature. After dipping for 10 seconds, the amount of wet film is controlled to a predetermined value by air blowing. Next, in a drying furnace, the heat exchanger itself was heated and baked so that the temperature of the heat exchanger itself was maintained at 140 ° C. for 5 minutes, thereby producing a test heat exchanger.
- Treatment II bath washing ⁇ chemical conversion treatment ⁇ hydrophilization treatment ⁇ baking
- the heat exchanger was washed with hot water at 50 ° C. for 30 seconds, in Examples 12 to 13 and Comparative Example 3, it was placed in a zirconium chemical conversion treatment bath having a Zr concentration of 500 ppm, a pH of 4 and a temperature of 60 ° C. for 60 seconds. Immersion treatment was performed and zirconium conversion treatment was performed.
- immersion treatment, air blowing, and baking treatment were performed in the same manner as in the above treatment I, to prepare a test heat exchanger.
- Example 1 (1) Preparation of hydrophilization treatment solution Lithium hydroxide as a lithium ion source and polyvinyl alcohol as a hydrophilic resin [degree of saponification: 99%, number average molecular weight: 60000] 2.0 parts and 2.0 parts of silica as an inorganic crosslinking agent were blended, and ion-exchanged water was added to make 100 parts to prepare a hydrophilization treatment liquid. (2) Production of test heat exchanger A test heat exchanger was produced according to the treatment I described above using the hydrophilization treatment liquid obtained in (1) above, and physical properties were evaluated. Table 1 shows the content of each component in the hydrophilization treatment liquid and the evaluation results of the physical properties.
- the coating amount of the hydrophilic coating in the test heat exchanger was 0.5 g / m 2 .
- the coating amount of the hydrophilic coating is calculated from the measured value of the TOC device (TOC-VCSH manufactured by Shimadzu Corporation) using a conversion factor calculated from the relationship between the hydrophilic coating amount of the standard coating sample and the amount of organic carbon contained therein. did.
- the lithium concentration in the hydrophilic film was 2.4% by mass.
- the lithium concentration in the hydrophilized film was measured by atomic absorption method after dissolving the hydrophilized film with acid.
- Examples 2 to 11, 14 to 16 and Comparative Examples 1 to 2, 4 to 5 Preparation of hydrophilization treatment liquid
- the hydrophilization treatment liquid was prepared in the same manner as in Example 1 (1) so that the content of each component in the hydrophilization treatment liquid became the values shown in Table 1 or Table 2.
- Example 2 lithium carbonate was used as the lithium ion source, and in Examples 3 to 11 and 14 to 16, lithium hydroxide was used as the lithium ion source.
- Example 1 and 2 no alkali metal ion source was added.
- lithium hydroxide was used as the lithium ion source, sodium hydroxide was used as the sodium ion source, and potassium hydroxide was used as the potassium ion source.
- test heat exchanger was produced in the same manner as in Example 1 (2), and physical properties were evaluated.
- the amount of the hydrophilized film in the test heat exchanger was 0.2 g / m 2 in Example 15, 2.0 g / m 2 in Example 16, and 0.5 g / m 2 in the others.
- Tables 1 and 2 show the evaluation results of the physical properties of the test heat exchanger, the coating amount of the hydrophilic coating, and the lithium concentration in the solid content, which is the lithium concentration in the hydrophilic coating.
- Examples 12 to 13 and Comparative Example 3 Preparation of hydrophilization treatment liquid
- the hydrophilization treatment liquid was prepared in the same manner as in Example 1 (1) so that the content of each component in the hydrophilization treatment liquid became the values shown in Table 1 or Table 2. Prepared.
- lithium hydroxide was used as the lithium ion source.
- (2) Production of test heat exchanger A test heat exchanger was produced in accordance with the treatment II described above using the hydrophilization treatment liquid obtained in (1) above. As a result of measuring the film amount of the hydrophilic film in this test heat exchanger in the same manner as in Example 1 (2), both were 0.5 g / m 2 .
- Tables 1 and 2 show the evaluation results of the physical properties of the test heat exchanger, the coating amount of the hydrophilic coating, and the lithium concentration in the solid content, which is the lithium concentration in the hydrophilic coating.
- the method for hydrophilizing a heat exchanger of the present invention is applied to an aluminum material heat exchanger flux-brazed by the NB method, particularly an aluminum material heat exchanger used in an air conditioner for automobiles,
- an aluminum material heat exchanger flux-brazed by the NB method particularly an aluminum material heat exchanger used in an air conditioner for automobiles
- a surface treatment with a hydrophilic treatment liquid containing lithium ions without subjecting the heat exchanger to a chemical conversion treatment in advance, the corrosion resistance can be greatly improved without impairing the hydrophilicity of the surface, and the deodorization property is also improved. Can be improved.
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Abstract
Description
さらに、アルミニウムフィンやアルミニウムチューブ(以下、「アルミニウムフィン等」という。)を構成するアルミニウムやその合金は、通常、本来防錆性に優れているが、凝縮水がフィン表面に長時間滞留すると、酸素濃淡電池を形成し、又は大気中の汚染成分が次第に付着、濃縮されて水和反応や腐食反応が促進される。この腐食生成物は、フィン表面に堆積し、熱交換特性を害するほか、白い微粉となって送風機により排出される。
しかしながら、近年、酸化皮膜を効果的に除去、破壊する手段としてハロゲン系フラックスが開発され、ろう付けの管理が容易、炉が安価、ろう付け加工のコストが安価などの理由で、窒素ガス中でろう付けするNB法に代表されるフラックスろう付け法が用いられるようになってきた。
このNB法は、アルミニウムフィン等を組み立てた後、KAlF4及びK2AlF5等のフラックスを用いて、窒素ガス中でアルミニウムフィン等をろう付けする方法であり、自動車用エアコンにおける熱交換器の作製にも適用されてきている。
ところが、このNB法で作製されたNB熱交換器は、アルミニウム表面にフラックスが不可避的に残存するために表面状態が不均一になり、化成処理、親水化処理等の均一な表面処理ができず、耐食性、密着性等が不充分になるというNB熱交換器特有の問題がある。
さらには、人体への安全性の問題からCr6+を配合しない化成処理が必要とされるが、その場合、耐食性が不充分である。またさらに、工程数の削減も求められていた。
一方、特許文献3に記載の熱交換器フィン用親水化処理剤は、ポリビニルアルコールと特定のアクリル樹脂を含むと共に、好ましくは珪酸リチウムを含むものである。この技術は、得られる皮膜の水接触角を低下させることで親水性向上による着霜防止を図ることにある。
しかし、引用文献3に開示されている親水化処理剤は、室外機の熱交換フィン材に対するものであり、親水化処理剤は、アルミニウムフィンを組み立てる前のアルミニウム板に対して施されるものであり、NB法で作製された熱交換器に対する親水化処理特有の上記問題は存在しない。
リチウムイオンは、腐食環境において、表面処理(親水化処理、化成処理)皮膜下で溶解したフラックスに作用し、Li2AlF5等として難溶化することにより、腐食起点を抑える効果を有すると考えられる。すなわち、本発明は、アルミニウム材上に残存するフラックスに作用することで、アルミニウム材製熱交換器の耐食性を向上させるものである。
本発明は、かかる知見に基づいて完成したものである。
(1)ノコロックろう付け法によりフラックスろう付けされたアルミニウム材製熱交換器に、親水化処理液を付着させた後、焼付け処理して、前記アルミニウム材製熱交換器の表面に親水化皮膜を形成させる耐食処理方法であって、
前記親水化処理液が、親水性樹脂及びリチウムイオンを含み、かつ前記親水化皮膜中のリチウム濃度が0.05~25質量%であるアルミニウム材製熱交換器の耐食処理方法、
(2)前記親水化皮膜の皮膜量が0.1~5.0g/m2である上記(1)に記載のアルミニウム材製熱交換器の耐食処理方法、
(3)熱交換器を予め化成処理した後、親水化処理液と接触させ、その後、焼付け処理する上記(1)又は(2)に記載のアルミニウム材製熱交換器の耐食処理方法、
(4)前記熱交換器が予め化成処理したものでないアルミニウム材製熱交換器である上記(1)又は(2)に記載のアルミニウム材製熱交換器の耐食処理方法、
(5)親水性樹脂が、ケン化度90%以上のポリビニルアルコール及び/又は変性ポリビニルアルコールである上記(1)~(4)のいずれかに記載のアルミニウム材製熱交換器の耐食処理方法、
(6)親水化処理液が、さらに架橋剤を含む上記(1)~(5)のいずれかに記載のアルミニウム材製熱交換器の耐食処理方法、
を提供するものである。
本発明は、NB熱交換器の表面に残存するフラックスに作用して、熱交換器の耐食性を大幅に向上させるものである。従って、本発明に用いる熱交換器は、NB法によりフラックスろう付けされたアルミニウム材製熱交換器である。当該熱交換器の表面には、フラックスが不可避的に残存する。
NB熱交換器としては、自動車の空調装置に用いられるアルミニウム材製熱交換器が挙げられる。なお、本発明において「アルミニウム材」とは、アルミニウム又はアルミニウム合金のことを指す。
当該熱交換器は、アルミニウム材製のフィン及びチューブが、窒素ガス中でろう付けする公知のNB法により接合されている。
NB法で用いるフラックスとしては、リチウムイオンと難溶性の塩を形成するアニオンで構成される塩を含むフラックスであれば特に限定されず、NB法で用いる通常のハロゲン系のフラックスを用いることができる。かかるハロゲン系のフラックスとしては、KAlF4、K2AlF5、K3AlF6、CsAlF4、Cs3AlF6及びCs2AlF5、並びに、これらのうち二種以上の混合物が挙げられる。
本発明においては、上記のようにして、アルミニウム材製のフィン及びチューブがNB法によりフラックスろう付けされて接合され、組み立てられた熱交換器を、親水化処理液と接触させたのち、焼付け処理して、表面に親水化皮膜を形成させ、親水化処理を行う。
(親水化処理液)
本発明で用いる親水化処理液は、水系溶媒中に親水性樹脂及びリチウムイオンを含む水系溶液又は水系分散液である。
親水性樹脂に特に制限はないが、分子内に水酸基、カルボキシル基、アミド基、アミノ基、スルホン酸基及び/又はエーテル基を有する水溶性又は水分散性の親水性樹脂であることが好ましい。上記親水性樹脂は、水滴との接触角が40度以下となるような皮膜を形成するものであることが好ましい。このような皮膜は良好な親水性を示すため、上記親水性樹脂を含む親水化処理液を適用すると、充分な親水性を被処理物に付与することができる。上記親水性樹脂としては、例えば、ポリビニルアルコール、ポリビニルピロリドン、ポリアクリル酸、ポリスチレンスルホン酸、ポリアクリルアミド、カルボキシメチルセルロース、キトサン、ポリエチレンオキサイド、水溶性ナイロン、これらの重合体を形成するモノマーの共重合体、2-メトキシポリエチレングリコールメタクリレート/アクリル酸2-ヒドロキシルエチル共重合体等のポリオキシエチレン鎖を有するアクリル系重合体等が好ましい。これらは一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
上記親水性樹脂は、数平均分子量が1000~100万の範囲内であることが好ましい。数平均分子量が1000以上であると、造膜性、親水性及び他の皮膜物性が良好であり、一方100万以下であると、親水化処理液の粘度が高くなりすぎることがなく、作業性や皮膜物性が良好となる。より好ましい数平均分子量は1万~20万の範囲である。
なお、本発明において、親水性樹脂の数平均分子量は、ゲルパーミエーションクロマトグラフィー法(GPC法)により測定された標準ポリスチレン換算の値である。
ケン化度90%以上のポリビニルアルコールは、もとより親水性付与の性能を有するが、耐水性が高い親水樹脂であり、アルミニウムフィンを緻密にコートでき、また樹脂の耐水性が高いため防臭性、付着臭抑制効果が高い。上記ケン化度は、上記効果の観点から95%以上であることが特に好ましい。ケン化度が90%未満であると、親水性に劣る場合がある。
本発明において、親水性樹脂として上記ケン化度が90%以上であるポリビニルアルコールを用いる場合には、その含有量は、上記効果の観点から、当該親水化処理液の全固形分に対し、10~90質量%であることが好ましく、20~80質量%であることがより好ましい。
上記変性ポリビニルアルコールとしては、ペンダント基中の0.01~20%が、下記一般式(1)
上記ポリオキシアルキレン変性ポリビニルアルコールにおいて、ポリオキシアルキレン変性基がペンダント基中の0.1~5%であることが好ましく、ポリオキシアルキレン基の重合度nは3~30であることが好ましい。
上記ポリオキシアルキレン変性ポリビニルアルコールは、ポリオキシアルキレン基の親水性ゆえに、当該親水化処理液において、特に親水性付与の役割を果たす。
なお、本発明において、親水性樹脂として、上記のケン化度90%以上のポリビニルアルコールと、上記ポリオキシアルキレン変性ポリビニルアルコールとを併用する場合、親水性と臭気性のバランスの観点から、両者の配合割合は、質量比で10:1~1:4の範囲であることが好ましく、5:1~1:3の範囲であることがより好ましい。両者を併用することにより、臭気性が良好で、親水持続性に優れた親水皮膜が得られる。
当該親水化処理液には、前述した親水性樹脂と共に、リチウムイオンを含む。このリチウムイオン源としては、親水化処理液中でリチウムイオンを形成し得るリチウム化合物であればよく、特に制限されず、例えば水酸化リチウム、硫酸リチウム、炭酸リチウム、硝酸リチウム、酢酸リチウム、クエン酸リチウム、乳酸リチウム、リン酸リチウム、シュウ酸リチウム、珪酸リチウム、メタ珪酸リチウムなどを用いることができる。中でも、臭気への影響が少ない点で、水酸化リチウム、硫酸リチウム、炭酸リチウムを用いることが好ましい。リチウムイオン源は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
本発明においては、このようにリチウムイオンを含む親水化処理液を用い、NB法によりフラックスろう付けされたアルミニウム材製熱交換器を表面処理して、親水化皮膜を形成させることにより、耐食性を大幅に向上させることができる。
イオン交換反応としては、例えば、次の式(2)のような反応が考えられる。
KxAlFy + xLi+ → LixAlFy + xK+ ・・・・(2)
(ただし、x及びyは、x=1のときy=4、x=2のときy=5またはx=3のときy=6である。)
また、親水化皮膜中のリチウムは長期間にわたって残存するので、上記効果は長期間にわたって持続し得る。
本発明においては、上記親水化皮膜中のリチウム濃度(全固形分中の濃度)は、耐食性の向上効果及び経済性のバランスなどの観点から、0.05~25質量%であり、好ましくは0.1~10質量%である。上記親水化皮膜中のリチウム濃度(全固形分中の濃度)が0.05質量%未満であると、耐食性が不十分であり、25質量%を超えても耐食性は向上せず、経済性が悪い。
当該親水化処理液には、それを用いて形成される親水化皮膜の耐水性を向上させる目的で、必要に応じ架橋剤を含有させることができる。
架橋剤としては、ポリビニルアルコールや変性ポリビニルアルコールの水酸基と反応する無機架橋剤や有機架橋剤を用いることができる。
無機架橋剤としては、二酸化珪素などのシリカ化合物、ジルコンフッ化アンモニウムやジルコン炭酸アンモニウムなどのジルコニウム化合物、チタンキレートなどの金属キレート化合物、Ca、Al、Mg、Fe、Znなどのリン酸塩、縮合リン酸などのリン系化合物等が挙げられる。
一方、有機架橋剤としては、メラミン樹脂、フェノール樹脂、エポキシ化合物、ブロック化イソシアネート化合物、オキサゾリン化合物、カルボジイミド化合物等が挙げられる。
これらの架橋剤は一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
本発明においては、上記架橋剤の含有量は、架橋効果及び経済性のバランスなどの観点から、当該親水化処理液の全固形分に対して、0.1~70質量%であることが好ましく、2~50質量%であることがより好ましい。
当該親水化処理液には、必要に応じグアニジン化合物及び/又はその塩を含有させることができる。
このグアニジン化合物は、下記一般式(3)
で表される化合物である。
上記グアニジン化合物としては特に限定されず、例えば、グアニジン、アミノグアニジン、グアニルチオ尿素、1,3-ジフェニルグアニジン、1,3-ジ-o-トリルグアニジン、1-o-トリルビグアニド、ポリヘキサメチレンビグアニジン、ポリヘキサエチレンビグアニジン、ポリペンタメチレンビグアニジン、ポリペンタエチレンビグアニジン、ポリビニルビグアニジン、ポリアリルビグアニジンなどを挙げることができる。これらのグアニジン化合物は、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。
また、本発明においては、グアニジン化合物を一種以上用いてもよいし、グアニジン化合物塩を一種以上用いてもよく、あるいはグアニジン化合物一種以上とグアニジン化合物塩一種以上とを併用してもよい。
このグアニジン化合物やその塩は、当該親水化処理液を用いて形成される親水化皮膜に優れた防錆性を付与する効果を有する。
なお、グアニジン化合物塩の質量平均分子量は、上記グアニジン化合物の質量平均分子量と、当該グアニジン化合物に付加した塩の合計分子量との和となる。
なお、上記グアニジン化合物の質量平均分子量はGPC法によって測定された標準ポリスチレン換算の値である。
当該親水化処理液には、他の任意成分として、必要に応じて、分散剤、防錆添加剤、顔料、シランカップリング剤、抗菌剤(防腐剤)、界面活性剤、潤滑剤、消臭剤などを適宜含有させることができる。
上記分散剤としては特に限定されず、界面活性剤や、分散樹脂などを挙げることができる。
上記シランカップリング剤としては特に限定されず、例えば、γ-アミノプロピルトリメトキシシラン、γ-アミノプロピルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-メタクリロキシプロピルトリエトキシシラン、N-〔2-(ビニルベンジルアミノ)エチル〕-3-アミノプロピルトリメトキシシラン等を挙げることができる。
上記抗菌剤(防腐剤)としては特に限定されず、例えば、2-(4-チアゾリル)ベンズイミダゾール、ジンクピリチオン、ベンゾイソチアゾリン等の従来公知の抗菌剤を使用することができる。
当該親水化処理液の溶媒は特に限定されないが、廃液処理等の観点から水を主体とする水系溶媒が好ましい。また、造膜性を向上させ、より均一で平滑な皮膜を形成するために溶剤を併用してもよい。溶剤としては、塗料に一般的に用いられ、水と均一に混合することができるものであれば特に限定されず、例えばアルコール系、ケトン系、エステル系、エーテル系の有機溶剤等を挙げることができる。上記溶剤の使用量は、当該親水化処理液中の該溶剤含有量が0.01~5質量%であることが好ましい。
当該親水化処理剤は、処理剤としての安定性を向上させるために、pHを調整してもよい。pHの調整は、硫酸、硝酸、アンモニア等の一般的な酸やアルカリで行うことができる。
当該親水化処理液中の全固形分濃度は、作業性、形成される親水化皮膜の均一性や厚さ、経済性などの観点から、1~11質量%が好ましく、より好ましくは2~5質量%である。また、当該親水化処理液中の親水性樹脂の濃度は、0.01~10質量%が好ましく、より好ましくは0.1~5質量%である。
上記親水性樹脂として、ケン化度が90%以上のポリビニルアルコールを用いる場合には、その濃度は、0.1~10質量%が好ましく、より好ましくは0.2~9.0質量%であり、ポリオキシアルキレン変性ポリビニルアルコールを用いる場合には、その濃度は、0.03~4.4質量%が好ましく、より好ましくは、0.05~3.3質量%である。
リチウムイオン濃度は、0.001~2.5質量%が好ましく、より好ましくは0.05~1.0質量%である。
また、任意成分の架橋剤を用いる場合、該架橋剤の濃度は、0.001~8質量%が好ましく、より好ましくは0.02~1.0質量%である。グアニジン化合物及び/又はその塩濃度は、0.01~5.5質量%が好ましく、より好ましくは0.02~3質量%である。
その他任意成分の合計濃度は、0.001~5質量%が好ましく、より好ましくは0.02~1質量%である。
本発明においては、NB法によりフラックスろう付けされたアルミニウム材製熱交換器(被処理物)を、前述した親水化処理液と接触させたのち、焼付け処理して、表面に親水化皮膜を形成させる防錆処理を行う。
被処理物は、親水化処理する前に、従来公知の方法で湯洗処理することが好ましい。
上記被処理物に親水化処理液を付着させる方法としては、浸漬法、スプレー法、塗布法などが挙げられるが、被処理物のNB熱交換器は複雑な形状を有することから浸漬法が好ましい。浸漬法を採用する場合、通常室温で10秒間程度浸漬処理する。形成される親水化皮膜の皮膜量は、エアブローによりウェットな状態での付着量をコントロールすることにより、制御することができる。
本発明においては、上記熱交換器を予め化成処理しなくても十分な耐食性を付与することができるが、さらに耐食性を向上させる目的で、所望により、上記熱交換器を予め化成処理した後、前述した方法により、リチウムイオン含有親水化処理液で親水化処理を施してもよい。
化成処理の方法としては、特に制限はなく、従来公知の各種化成処理を用いることができるが、人体への安全性の問題から、Cr6+を配合しない化成処理が好ましい。このような化成処理としては、例えばジルコニウム化成処理やチタニウム化成処理などを挙げることができる。この化成処理は、被処理物であるNB熱交換器を湯洗処理後、行うことが望ましい。
以下は、ジルコニウム化成処理をとり上げ説明する。
ジルコニウム化成処理は、ジルコニウムを含有するpH3~5のジルコニウム化成処理液で上記被処理物を処理するものである。
本発明に用いるジルコニウムを含有するジルコニウム化成処理液は、ジルコニウム系化合物を水に溶解して、ジルコニウムイオンを活性種とする溶液である。ジルコニウム系化合物としては、フルオロジルコニウム酸、フッ化ジルコニウム等のジルコニウム化合物、およびそれらのリチウム、ナトリウム、カリウム、アンモニウム等の塩が挙げられる。また酸化ジルコニウム等のジルコニウム化合物をフッ化水素酸等のフッ化物で溶解させてもよい。
このジルコニウム化成処理液のジルコニウムの含有量は特に限定されないが、50~5000ppmが好ましく、100~3000ppmがより好ましく、300~1500ppmがさらに好ましい。NB熱交換器のアルミニウム材表面上のジルコニウム化成皮膜の量は、防錆性の観点から、好ましくは1~200mg/m2であり、より好ましくは2~150mg/m2である。
また、このジルコニウム化成処理液は、上記ジルコニウム系化合物の他に、防錆性を向上させるために、チタン、マンガン、亜鉛、セリウム、バナジウム、3価クロム等の金属イオン、フェノール樹脂等の防錆剤;密着性向上のためのシランカップリング剤;化成反応促進のためのリン酸等が含有されていてもよい。
また、ジルコニウム化成処理液の温度は、好ましくは50~70℃であり、より好ましくは55~65℃である。また、ジルコニウム化成処理の時間は、好ましくは20~900秒であり、より好ましくは30~600秒である。この範囲の処理液の温度及び処理の時間であれば、防錆性を有するジルコニウム化成皮膜を形成することができる。
なお、各例で得られた親水化処理液を用いて親水化処理された試験熱交換器について、以下に示す物性評価を行った。
JIS Z 2371に基づき、5質量%食塩水を35℃にて噴霧し、500時間後の白錆発生面積を下記の評価基準に基づき、0.5刻みで目視評価した。
耐食性評価は、8以上であることが好ましい。
10:白錆発生なし
9:白錆発生面積が10%未満
8:同20%未満
7:同30%未満
6:同40%未満
5:同50%未満
4:同60%未満
3:同70%未満
2:同80%未満
1:同90%未満
試験熱交換器を流水に72時間接触させた後、水滴との接触角を測定した。接触角が小さい程、親水性が高いと考えられる。接触角の測定は、自動接触角計「CA-Z」(協和界面化学社製)を用いて行った。
親水性は、接触角が40°以下であることが好ましい。
試験熱交換器を水道水流水に72時間接触させた後、臭いを嗅いで、下記評価基準に基づき6段階評価した。当該評価を5人の評価者が行い、平均値を算出した。臭気は2.0以下であることが好ましく、1.5以下であることがより好ましい。
0:無臭
1:やっとかすかに臭いを感じる
2:らくに臭いを感じる
3:明らかに臭いを感じる
4:強く臭いを感じる
5:非常に強く臭いを感じる
熱交換器としては、KAlF4及びK3AlF6のフラックスでろう付けされた自動車用のアルミニウム材製熱交換器(NB熱交換器)を用いた。この熱交換器の、フラックス量は、Kとして50mg/m2(フィン表面)であった。
この熱交換器について、下記の処理I又は処理IIを施して、試験熱交換器を作製した。
上記熱交換器を、50℃の温水で30秒間湯洗したのち、実施例1~11、14~16及び比較例1~2、4~5で得られた親水化処理液の浴中に室温で10秒間浸漬後、エアブローによりウェット皮膜量を所定の値に制御する。次いで乾燥炉にて、熱交換器自体の温度が140℃にて5分間維持されるように加熱して焼付け処理し、試験熱交換器を作製した。
上記熱交換器を、50℃の温水で30秒間湯洗したのち、実施例12~13及び比較例3においては、Zr濃度500ppm、pH4、温度60℃のジルコニウム化成処理液の浴中に60秒間浸漬処理して、ジルコニウム化成処理した。次いで実施例12~13及び比較例3で得られた親水化処理液をそれぞれ用いて、上記の処理Iと同様にして浸漬処理、エアブロー、焼付け処理を施し、試験熱交換器を作製した。
(1)親水化処理液の調製
リチウムイオンが0.1部となるように、リチウムイオン源としての水酸化リチウムと、親水性樹脂であるポリビニルアルコール[ケン化度:99%、数平均分子量:60000]2.0部と、無機架橋剤であるシリカ2.0部を配合し、イオン交換水を加えて100部とし、親水化処理液を調製した。
(2)試験熱交換器の作製
上記(1)で得られた親水化処理液を用い、前述した処理Iに従い、試験熱交換器を作製し、物性の評価を行った。親水化処理液中の各成分の含有量及び物性の評価結果を表1に示す。
試験熱交換器における親水化皮膜の皮膜量は、0.5g/m2であった。親水化皮膜の皮膜量は、標準皮膜サンプルの親水皮膜量とこれに含まれる有機炭素量の関係から算出した換算係数を用いて、TOC装置(島津製作所社製TOC-VCSH)の測定値から計算した。
また、親水化皮膜中のリチウム濃度は2.4質量%であった。親水化皮膜中のリチウム濃度は、親水化皮膜を酸により溶解し、原子吸光法により測定した。
(1)親水化処理液の調製
親水化処理液中の各成分の含有量が、表1または表2に示す値になるように、実施例1(1)と同様にして親水化処理液を調製した。
なお、実施例2の場合、リチウムイオン源として炭酸リチウムを用い、実施例3~11、及び14~16の場合、リチウムイオン源として水酸化リチウムを用いた。比較例1及び2では、アルカリ金属イオン源を添加しなかった。また、比較例4~5の場合、リチウムイオン源として水酸化リチウム、ナトリウムイオン源として水酸化ナトリウム、カリウムイオン源として水酸化カリウムを用いた。
(2)試験熱交換器の作製
実施例1(2)と同様にして試験熱交換器を作製し、物性の評価を行った。なお、試験熱交換器における親水化皮膜の皮膜量は、実施例15は0.2g/m2、実施例16は2.0g/m2、その他は0.5g/m2であった。
試験熱交換器の物性の評価結果及び親水化皮膜の皮膜量、親水化皮膜中のリチウム濃度である固形分中のリチウム濃度を表1、表2に示す。
(1)親水化処理液の調製
親水化処理液中の各成分の含有量が、表1または表2に示す値になるように、実施例1(1)と同様にして親水化処理液を調製した。
なお、実施例12~13の場合、リチウムイオン源として水酸化リチウムを用いた。
(2)試験熱交換器の作製
上記(1)で得られた親水化処理液を用い、前述した処理IIに従い、試験熱交換器を作製した。
この試験熱交換器における親水化皮膜の皮膜量を、実施例1(2)と同様にして測定した結果、いずれも0.5g/m2であった。
試験熱交換器の物性の評価結果及び親水化皮膜の皮膜量、親水化皮膜中のリチウム濃度である固形分中のリチウム濃度を表1、表2に示す。
1)ポリビニルアルコール:[ケン化度:99%、数平均分子量:60000]
2)エチレンオキサイド変性ポリビニルアルコール:[ケン化度:99%、数平均分子量:20000、ポリオキシエチレン基の含有割合(ポリビニルアルコールの全ペンダント基に対する割合):3%、ポリオキシエチレン基におけるオキシエチレン基の繰り返し数(重合度):10]
3)カルボキシメチルセルロース:[数平均分子量:10000]
4)ポリビニルスルホン酸ナトリウム:[数平均分子量:20000]
5)ポリアクリル酸:[数平均分子量:20000]
6)シリカ(無水シリカ):[1次粒子の平均径:10nm]、無機架橋剤
7)ジルコンフッ化アンモニウム、無機架橋剤
8)フェノール樹脂:[レゾール型フェノール]、有機架橋剤
9)ポリヘキサメチレンビグアニジン:[質量平均分子量:5000]
なお、表1および表2において、かっこで記載されている親水性皮膜中のリチウム、親水性皮膜中のナトリウム及び親水性皮膜中のカリウムの値は、それぞれ、親水化皮膜中(固形分中)のリチウム、ナトリウム及びカリウムの濃度(質量%)である。また、表1および表2において、かっこで記載されている上記以外の成分の値は、それぞれ、親水化処理液の全固形分中の質量%である。
また、実施例12及び13と他の実施例との比較から、熱交換器を予め化成処理したのち、親水化処理することにより、耐食性がさらに向上することがわかる。
Claims (6)
- ノコロックろう付け法によりフラックスろう付けされたアルミニウム材製熱交換器に、親水化処理液を付着させた後、焼付け処理して、前記アルミニウム材製熱交換器の表面に親水化皮膜を形成させる耐食処理方法であって、
前記親水化処理液が、親水性樹脂及びリチウムイオンを含み、かつ前記親水化皮膜中のリチウム濃度が0.05~25質量%であるアルミニウム材製熱交換器の耐食処理方法。 - 前記親水化皮膜の皮膜量が0.1~5.0g/m2である請求項1に記載のアルミニウム材製熱交換器の耐食処理方法。
- 熱交換器を予め化成処理した後、親水化処理液と接触させ、その後、焼付け処理する請求項1又は2に記載のアルミニウム材製熱交換器の耐食処理方法。
- 前記熱交換器が予め化成処理したものでないアルミニウム材製熱交換器である請求項1又は2に記載のアルミニウム材製熱交換器の耐食処理方法。
- 親水性樹脂が、ケン化度90%以上のポリビニルアルコール及び/又は変性ポリビニルアルコールである請求項1~4のいずれかに記載のアルミニウム材製熱交換器の耐食処理方法。
- 親水化処理液が、さらに架橋剤を含む請求項1~5のいずれかに記載のアルミニウム材製熱交換器の耐食処理方法。
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Application Number | Priority Date | Filing Date | Title |
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US13/512,614 US9139913B2 (en) | 2009-11-30 | 2010-11-26 | Anti-corrosion treatment method for aluminum heat exchanger |
RU2012126849/02A RU2012126849A (ru) | 2009-11-30 | 2010-11-26 | Способ антикоррозийной обработки алюминиевого теплообменника |
CN201080054133.7A CN102892927B (zh) | 2009-11-30 | 2010-11-26 | 铝材制热交换器的耐腐蚀处理方法 |
EP10833328.7A EP2508647B1 (en) | 2009-11-30 | 2010-11-26 | Anti-corrosion treatment method for aluminium heat exchanger |
AU2010323484A AU2010323484A1 (en) | 2009-11-30 | 2010-11-26 | Anti-corrosion treatment method for aluminium heat exchanger |
BR112012012976A BR112012012976A2 (pt) | 2009-11-30 | 2010-11-26 | método de tratamento anticorrosão para trocador de calor de alumínio |
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PCT/JP2010/071129 WO2011065482A1 (ja) | 2009-11-30 | 2010-11-26 | アルミニウム材製熱交換器の耐食処理方法 |
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US (1) | US9139913B2 (ja) |
EP (1) | EP2508647B1 (ja) |
JP (1) | JP5794512B2 (ja) |
CN (1) | CN102892927B (ja) |
AU (1) | AU2010323484A1 (ja) |
BR (1) | BR112012012976A2 (ja) |
CZ (1) | CZ2012334A3 (ja) |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9739544B2 (en) | 2012-03-09 | 2017-08-22 | Nippon Paint Surf Chemicals Co., Ltd. | Surface treatment method for aluminum heat exchangers |
US9757811B2 (en) | 2011-09-21 | 2017-09-12 | Nippon Paint Surf Chemicals Co., Ltd. | Method for treating surface of aluminum heat exchanger |
US9896766B2 (en) | 2013-04-03 | 2018-02-20 | Nippon Paint Surf Chemicals Co., Ltd. | Surface processing method for aluminum heat exchanger |
Families Citing this family (9)
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CA2906521C (en) * | 2013-03-16 | 2019-12-03 | Prc-Desoto International, Inc. | Azole compounds as corrosion inhibitors |
JP6300341B2 (ja) * | 2013-03-29 | 2018-03-28 | 株式会社神戸製鋼所 | アルミニウムフィン材 |
JP2016084382A (ja) * | 2014-10-23 | 2016-05-19 | シャープ株式会社 | 表面処理剤 |
JP6466144B2 (ja) * | 2014-11-14 | 2019-02-06 | ダイセルポリマー株式会社 | 水性表面処理剤及び被覆シート並びに塗布性改善方法 |
CN104588303A (zh) * | 2014-12-31 | 2015-05-06 | 东莞市高明企业服务有限公司 | 一种铝散热片的亲水性皮膜的制作工艺 |
EP3054235A1 (en) * | 2015-02-09 | 2016-08-10 | Ariston Thermo S.p.A. | Coating method for metal tanks with coil-wound heat exchanger |
JP2017082266A (ja) * | 2015-10-26 | 2017-05-18 | 株式会社神戸製鋼所 | 表面処理アルミニウム合金及び表面処理アルミニウム合金クラッド材 |
US10889723B2 (en) * | 2018-11-08 | 2021-01-12 | The United States Of America As Represented By The Secretary Of The Navy | Synergistic corrosion inhibitor compositions |
DE102019209249A1 (de) * | 2019-06-26 | 2020-12-31 | Mahle International Gmbh | Verfahren zum Passivieren einer mit einem Flussmittel versehenen Aluminiumoberfläche |
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JPH06300482A (ja) * | 1991-06-19 | 1994-10-28 | Nippon Parkerizing Co Ltd | 熱交換器 |
JP2001164175A (ja) | 1999-12-09 | 2001-06-19 | Kansai Paint Co Ltd | 熱交換器フィン材用親水化処理剤 |
JP2003003282A (ja) | 2001-03-27 | 2003-01-08 | Denso Corp | 親水化処理方法及び親水化処理された熱交換器 |
JP2006069197A (ja) | 2004-08-06 | 2006-03-16 | Nippon Paint Co Ltd | フラックスろう付けされたアルミ熱交換器の表面処理方法 |
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EP1624274B1 (en) * | 2004-08-06 | 2007-07-11 | Nippon Paint Co., Ltd. | Surface treatment method for flux-brazed aluminum-made heat exchanger |
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2010
- 2010-10-15 JP JP2010232824A patent/JP5794512B2/ja active Active
- 2010-11-26 CN CN201080054133.7A patent/CN102892927B/zh active Active
- 2010-11-26 WO PCT/JP2010/071129 patent/WO2011065482A1/ja active Application Filing
- 2010-11-26 CZ CZ20120334A patent/CZ2012334A3/cs unknown
- 2010-11-26 EP EP10833328.7A patent/EP2508647B1/en active Active
- 2010-11-26 BR BR112012012976A patent/BR112012012976A2/pt not_active IP Right Cessation
- 2010-11-26 AU AU2010323484A patent/AU2010323484A1/en not_active Abandoned
- 2010-11-26 US US13/512,614 patent/US9139913B2/en active Active
- 2010-11-26 RU RU2012126849/02A patent/RU2012126849A/ru not_active Application Discontinuation
Patent Citations (4)
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JPH06300482A (ja) * | 1991-06-19 | 1994-10-28 | Nippon Parkerizing Co Ltd | 熱交換器 |
JP2001164175A (ja) | 1999-12-09 | 2001-06-19 | Kansai Paint Co Ltd | 熱交換器フィン材用親水化処理剤 |
JP2003003282A (ja) | 2001-03-27 | 2003-01-08 | Denso Corp | 親水化処理方法及び親水化処理された熱交換器 |
JP2006069197A (ja) | 2004-08-06 | 2006-03-16 | Nippon Paint Co Ltd | フラックスろう付けされたアルミ熱交換器の表面処理方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US9757811B2 (en) | 2011-09-21 | 2017-09-12 | Nippon Paint Surf Chemicals Co., Ltd. | Method for treating surface of aluminum heat exchanger |
US9739544B2 (en) | 2012-03-09 | 2017-08-22 | Nippon Paint Surf Chemicals Co., Ltd. | Surface treatment method for aluminum heat exchangers |
US9896766B2 (en) | 2013-04-03 | 2018-02-20 | Nippon Paint Surf Chemicals Co., Ltd. | Surface processing method for aluminum heat exchanger |
Also Published As
Publication number | Publication date |
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BR112012012976A2 (pt) | 2017-03-01 |
US9139913B2 (en) | 2015-09-22 |
EP2508647A1 (en) | 2012-10-10 |
AU2010323484A1 (en) | 2012-06-14 |
JP2011131206A (ja) | 2011-07-07 |
CZ2012334A3 (cs) | 2012-09-19 |
EP2508647A4 (en) | 2017-01-04 |
CN102892927A (zh) | 2013-01-23 |
US20120288634A1 (en) | 2012-11-15 |
JP5794512B2 (ja) | 2015-10-14 |
EP2508647B1 (en) | 2018-07-18 |
RU2012126849A (ru) | 2014-01-10 |
CN102892927B (zh) | 2014-08-20 |
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