WO2011071105A1 - Matériau en aluminium revêtu et procédé pour sa fabrication - Google Patents

Matériau en aluminium revêtu et procédé pour sa fabrication Download PDF

Info

Publication number
WO2011071105A1
WO2011071105A1 PCT/JP2010/072109 JP2010072109W WO2011071105A1 WO 2011071105 A1 WO2011071105 A1 WO 2011071105A1 JP 2010072109 W JP2010072109 W JP 2010072109W WO 2011071105 A1 WO2011071105 A1 WO 2011071105A1
Authority
WO
WIPO (PCT)
Prior art keywords
aluminum
coating material
coating
coating film
concave
Prior art date
Application number
PCT/JP2010/072109
Other languages
English (en)
Japanese (ja)
Inventor
令子 高澤
正憲 遠藤
Original Assignee
日本軽金属株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日本軽金属株式会社 filed Critical 日本軽金属株式会社
Publication of WO2011071105A1 publication Critical patent/WO2011071105A1/fr

Links

Images

Classifications

    • 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
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/20—Acidic compositions for etching aluminium or alloys thereof
    • 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
    • C23C22/78—Pretreatment of the material to be coated
    • 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

Definitions

  • the present invention relates to an aluminum coating material including an aluminum shape body made of aluminum or an aluminum alloy and a coating film integrally provided by coating on the surface of the aluminum shape body, and a method for manufacturing the same, and is not particularly limited.
  • the present invention relates to a chromium-free aluminum coating material excellent in adhesion strength and corrosion resistance that can be suitably used in a wide range of fields, and a method for producing the same.
  • the present inventors can form a coating layer having not only high coating film hardness but also excellent coating adhesion and impact resistance, and thereby corrosion resistance, weather resistance, workability
  • the present inventors have proposed a method for producing a surface-treated aluminum material that can produce a surface-treated aluminum material that exhibits excellent performance in coating film hardness, coating film adhesion, and impact resistance (see Patent Documents 6 to 9).
  • These aluminum coating materials according to the present inventors can achieve their purpose, but when exposed to harsh environments such as temperature, humidity, dust, corrosive substances, etc. Compared to the chromate-treated aluminum coating material, the adhesion strength and corrosion resistance at the aluminum-coating interface are not always sufficient, and it is chromium-free and has better adhesion strength, corrosion resistance, and airtightness. Development of coating materials was requested.
  • the present inventors have extremely high adhesion strength and airtightness at the interface between an aluminum shape body made of aluminum or an aluminum alloy and a coating film integrally provided on the surface thereof, and excellent durability.
  • the aluminum shape body and chromium are formed by forming a specific surface shape having a concave portion on the surface of the aluminum shape body by etching treatment.
  • the present inventors have found that the adhesion and corrosion resistance with a free coating film are remarkably improved.
  • the object of the present invention is to provide extremely high adhesion at the interface between the aluminum body made of aluminum or aluminum alloy integrally bonded by coating and the coating film, and maintain excellent corrosion resistance in harsh environments. And providing a chromium-free aluminum coating material capable of exhibiting excellent durability.
  • Another object of the present invention is such that the adhesion and air tightness of the interface between the aluminum shaped body and the coating film are extremely high, maintaining excellent corrosion resistance even in harsh environments, and excellent durability.
  • An object of the present invention is to provide a method for producing an aluminum coating material capable of producing a chromium-free aluminum coating material capable of exhibiting the above.
  • the present invention relates to an aluminum including an aluminum-shaped body made of aluminum or an aluminum alloy having a concavo-convex portion on a part or the entire surface thereof, and a coating film coated on the surface of the aluminum-shaped body and bonded in a butt state. It is a coating material, and a plurality of concave portions due to the uneven portions are formed on the surface of the aluminum-shaped body, and a coating portion into which the paint has entered and solidified is formed in these concave portions.
  • the aluminum coating material is characterized in that the aluminum-shaped body and the coating film are locked to each other by the concave portion and the fitting portion.
  • the present invention also relates to an injection-integrated molded article comprising an aluminum-shaped body made of an aluminum alloy having a concavo-convex portion on a part or the entire surface thereof, and a coating film integrally provided on the surface of the aluminum-shaped body by coating.
  • a plurality of concave portions are formed on the surface of the aluminum shaped body due to the uneven portions, and each concave portion is orthogonal to the thickness direction in the cross section in the thickness direction of the aluminum shaped body.
  • the opening width measured by scanning electron microscope observation is 0.1 ⁇ m or more and 30 ⁇ m or less.
  • the depth is 0.1 ⁇ m or more and 30 ⁇ m or less, and in these concave portions, coating portions into which the paint has entered and solidified are formed, and the concave portions and the insertion portions are formed.
  • aluminum shape body Is aluminum coated material, characterized in that the coating is engaged with each other.
  • this invention is a manufacturing method of the aluminum coating material containing the aluminum shape body made from aluminum or aluminum alloy, and the coating film provided by coating on the surface of this aluminum shape body, and etches aluminum or aluminum alloy material
  • An aluminum shape body having a plurality of concave portions due to uneven portions is formed on a part or the entire surface of the surface, and when the coating film is formed, the paint enters the concave portions of the aluminum shape body and solidifies the coating film
  • the aluminum is characterized in that the fitting portion is formed, and the aluminum-shaped body and the coating portion are engaged with each other to form an aluminum coating material in which the aluminum shape body and the coating film are integrally bonded. It is a manufacturing method of a coating material.
  • examples of the aluminum or aluminum alloy material for forming the aluminum shaped body include a rolled material, an extruded shape material, a die-cast material, and a casting material.
  • the plurality of concave portions formed on the surface of the aluminum shape body due to the uneven portions on the surface of the aluminum shape body have a hole shape or an opening edge portion which is an endless peripheral portion. It may be a hole (a concave part having an endless opening edge), or a slit or groove having an opening edge having both ends (a concave part having an end opening edge) Further, a hole-like or hole-like one having these endless opening edges and a slit-like or groove-like one having endless opening edges may be mixed.
  • the protrusion part protruded in the shape of a snow flake toward the opening width direction center from a part or all part of the opening edge part of a recessed part preferably is formed.
  • the opening width of the concave portion is narrower than the width of the inside of the concave portion, and the inserted portions of the coating film that has entered and solidified into the concave portion are detached from each other.
  • FIG. 1 schematically showing a cross section of an aluminum-shaped body.
  • the plurality of concave portions 3 formed due to the uneven portions on the surface of the aluminum-shaped body 1 are formed of an aluminum-shaped body.
  • the aperture width (d) measured by observation with a scanning electron microscope is 0.1 ⁇ m or more and 30 ⁇ m or less, preferably 0.5 ⁇ m or more and 20 ⁇ m or less, more preferably 1 ⁇ m or more and 10 ⁇ m or less, and the depth is The size is 0.1 ⁇ m or more and 30 ⁇ m or less, preferably 0.5 ⁇ m or more and 20 ⁇ m or less.
  • the opening width (d) of the concave portion is smaller than 0.1 ⁇ m, it is difficult for the paint to enter at the time of coating, and a minute gap is generated at the interface between the aluminum body 1 and the coating film, and excellent adhesion and corrosion resistance.
  • the dissolution reaction proceeds excessively during the surface treatment (etching treatment) of the aluminum shaped body 1, which means that the material surface is lost or the material thickness is increased. Problems arise, products with insufficient material strength occur, and productivity is reduced.
  • the depth is less than 0.1 ⁇ m, it is difficult to obtain a sufficient coating portion, and conversely, if the depth is more than 30 ⁇ m, the aluminum body 1 is dissolved during the surface treatment (etching treatment). The reaction proceeds excessively, causing a problem that the surface of the material is missing or the thickness of the material is increased.
  • the density of the plurality of recessed portions formed due to the uneven portions on the surface of the aluminum-shaped body is in the range of an opening width of 0.5 to 20 ⁇ m and a depth of 0.5 to 20 ⁇ m per 0.1 mm square. It is preferable that one or two or more of them have a size of about 5 to 200.
  • the snow candy-like protruding portion formed in the concave portion is preferably thicker from the coating film side toward the aluminum shaped body side in the cross section in the thickness direction of the aluminum coating material.
  • a plurality of observation lines extending in the direction are drawn at an interval of 0.1 ⁇ m, at least one laminated portion composed of a coating film-aluminum-coating film is formed on one observation line, and the laminated portion
  • the thickness of the aluminum-shaped body portion of the aluminum coating material is preferably in the range of 0.1 ⁇ m or more and 30 ⁇ m or less, and the aluminum coating material has one such snow ridge-like protrusion within the range of 1000 observation lines. It should be present.
  • the plurality of concave portions of the aluminum-shaped body may have a double concave portion structure in which at least one or more internal concave portions are formed on the inner wall surface in part or all of the concave portions, It may have an internal concavo-convex structure in which at least one or more internal protrusions are formed on the inner wall surface, and these double concave structure and internal concavo-convex structure may coexist. Due to the presence of such a double-concave structure or internal concavo-convex structure in some or all of the plurality of concave parts of the aluminum-shaped body, the concave-shaped part of the aluminum-shaped body and the fitting part of the coating film are stronger together. Bonding to, it exhibits better adhesion and corrosion resistance between the aluminum shaped body and the coating film.
  • an aluminum shape body having a plurality of desired concave portions described above is formed on the surface.
  • an aluminum alloy material is used as a method thereof. A method of forming an uneven portion on a part or the entire surface by performing an etching process, and forming an aluminum shape body having a plurality of recessed portions due to the uneven portion.
  • Etching solutions used for etching the aluminum alloy material include, for example, hydrochloric acid, phosphoric acid, sulfuric acid, acetic acid, oxalic acid, ascorbic acid, benzoic acid, butyric acid, citric acid, formic acid, lactic acid, isobutyric acid, malic acid.
  • An etching solution composed of an aqueous acid solution such as propionic acid or tartaric acid can be mentioned, but a plurality of concave portions having a desired size in opening width and depth, or a part or all of the concave portions
  • a desired shape and size such as forming a snow ridge-like protruding portion that protrudes toward the opening width direction center at the opening edge of the
  • an acid aqueous solution having a weak oxidizing power and in such an acid aqueous solution having a relatively weak oxidizing power, It is necessary to the use of an etching solution containing at a given concentration Gen'ion.
  • An etching solution containing the above halogen ions in a predetermined concentration range is preferably used. Then, using such an aqueous acid solution containing a relatively weak oxidizing power containing halogen ions, and immersing the aluminum alloy material in this etching solution, the halogen ions in the etching solution first dissolve the oxide film on the surface of the aluminum alloy material. After that, the inner aluminum alloy is melted and further eroded into the aluminum alloy material.
  • the inner aluminum alloy is more easily eroded (dissolved) than the surface oxide film. Then, by setting the composition of the etching solution, the conditions for the etching process, etc., the opening width, depth, etc. of the concave portions due to the concave and convex portions formed on the surface can be controlled to a desired size, A snow candy-like protruding portion that protrudes toward the center in the opening width direction can be formed on a part or all of the opening edge.
  • an aqueous hydrochloric acid solution having an acid concentration of 0.1 to 80% by weight, preferably 0.5 to 50% by weight, phosphoric acid
  • halides added for introducing halogen ions include chlorides such as sodium chloride, potassium chloride, magnesium chloride, and aluminum chloride, fluorides such as calcium fluoride, and bromides such as potassium bromide.
  • the halogen ion concentration in the etching solution is usually 0.5 g / liter (g / L) to 300 g / L, preferably 1 g / L to 200 g / L, preferably 0.5 g. If it is less than / L, the effect of halogen ions is small, so that there is a problem that a concave portion having a snow ridge-like protrusion is not formed at the opening edge, and if it exceeds 300 g / L, the surface of the aluminum-shaped body Since the dissolution reaction proceeds rapidly during the processing (etching processing), there arises a problem that it becomes difficult to control the concave portion.
  • an etching solution for forming a desired concave portion on the surface of the aluminum-shaped body may be an aqueous solution or water of a relatively strong oxidizing power such as nitric acid or concentrated sulfuric acid having a concentration exceeding 80% by weight.
  • aqueous solution of an alkali such as sodium oxide or potassium hydroxide is not suitable.
  • An acid aqueous solution having a relatively strong oxidizing power has a film forming ability with respect to an aluminum alloy. On the contrary, a strong oxide film is formed on the surface of the aluminum shaped body, and it becomes difficult to dissolve the oxide film by halogen ions.
  • the dissolution mechanism of an aqueous alkali solution such as sodium hydroxide or potassium hydroxide is the entire surface dissolution type, and the tendency does not change even when halogen ions are added, and the desired shape and size are obtained. It becomes difficult to form the concave portion.
  • the processing conditions for etching the surface of the aluminum alloy material using the above etching solution are required for the type of etching solution used, the acid concentration, the halogen ion concentration, etc., and the aluminum shape.
  • the bath temperature is usually 20 to 80 ° C. for a hydrochloric acid aqueous solution and the immersion time is 1 to 30 minutes, and the bath temperature is 30 to 80 ° C. for a phosphoric acid aqueous solution.
  • the bath temperature is preferably 50 to 80 ° C. and the immersion time is 1 to 3 minutes. The higher the acid concentration and bath temperature of the etching solution to be used, the more effective the etching process becomes and the shorter the processing time is possible.
  • the dissolution reaction proceeds rapidly, making it difficult to control the opening width and depth of the concave portion.
  • the immersion time if the opening time is less than 1 minute, it is difficult to control the opening width and depth of the concave portion, and conversely, if the immersion time exceeds 30 minutes, the productivity is lowered.
  • the surface of the aluminum alloy material before the etching treatment is degreased, surface-adjusted, surface
  • a pretreatment consisting of an acid treatment with an acid aqueous solution and / or an alkali treatment with an alkali solution may be performed.
  • examples of the acid aqueous solution used for this pretreatment include those prepared with commercially available acid degreasing agents, mineral acids such as sulfuric acid, nitric acid, hydrofluoric acid, and phosphoric acid, organic acids such as acetic acid and citric acid, and the like.
  • acid reagents such as a mixed acid obtained by mixing acid
  • alkaline aqueous solution for example, what was prepared with a commercially available alkaline degreasing agent, caustic soda, etc.
  • alkali reagent, or what was prepared by mixing these things etc. can be used.
  • the operation method and treatment conditions of the pretreatment conventionally performed using this type of acid aqueous solution or alkali aqueous solution and For example, it can be performed by a method such as an immersion method or a spray method.
  • the aluminum alloy material that has been subjected to pretreatment and etching treatment is subjected to drying treatment as necessary.
  • This drying treatment may be natural drying that is allowed to stand at room temperature, or may be air blow, dryer, oven, etc. Forced drying may be used.
  • the surface of the aluminum shaped body obtained by the above etching treatment or by the pretreatment and the etching treatment has uneven portions formed by the etching treatment, and the surface has a 60 degree surface glossiness (handy gloss meter manufactured by Suga Test Instruments Co., Ltd.). Is preferably 60 or less. When the surface glossiness exceeds 60, the paint does not sufficiently enter the concave portion of the aluminum shaped body during painting, and sufficient adhesion between the aluminum shaped body and the coating film cannot be obtained.
  • the surface of the aluminum shaped body obtained by the above etching treatment or by the pretreatment and the etching treatment is observed with a SEM or an optical microscope at a magnification of 1000 times, and the obtained cross-sectional observation photograph is preferably an aluminum shape.
  • the surface area of the body is preferably 1.2 times or more and 10 times or less the surface area of the aluminum alloy material before forming the irregularities by etching treatment. When this surface area increase rate is less than 1.2 times or more than 10 times, the paint does not sufficiently enter the concave portion of the aluminum shape body during painting or painting, and between the aluminum shape body and the coating film. Sufficient adhesion cannot be obtained.
  • a paint film is formed by painting a paint on the aluminum shaped body obtained as described above.
  • a ground treatment may be performed.
  • an acid solution and / or an alkali solution containing a silicon compound or a commercially available chromium-free treatment agent may be used.
  • the acid solution and / or alkali solution containing such a silicon compound include an acid solution containing colloidal silica and an alkali solution containing a silicate such as sodium metasilicate.
  • commercially available chromium-free treatment agents include Alsurf and Surfcoat manufactured by Nippon Paint, and Palcoat manufactured by Nippon Parkerizing.
  • the coating method of this paint for example, roll coating method, spray coating method, dipping method, curtain flow coater method, bar coating method, electrostatic coating method, powder coating method, spin coating method, brush coating, roller coating, etc.
  • the pre-coating method or the post-coating method may be used.
  • adopt the drying method according to a coating material for example, performing normal temperature drying or baking drying using an air blow, a dryer, oven, etc., and the range of room temperature to 300 degreeC
  • the method of performing 5 seconds to 24 hours can be exemplified.
  • the target aluminum coating material is manufactured by forming a coating film on the aluminum shape.
  • a particularly preferable aluminum coating material is an aluminum coating material including a coating film bonded to a part of the surface of an aluminum shaped body by a coating.
  • the coating film formed on the surface of the aluminum shape material is not particularly limited.
  • the coating material for forming this coating film include acrylic coating materials, polyester coating materials, and urethane coating materials. Paint, acrylic urethane, acrylic polyester, epoxy paint, fluorine paint, alkyd paint, amino alkyd paint, vinyl paint, chlorinated rubber paint, silicone paint, acrylic silicone paint, urethane silicone paint, Examples include acrylic urethane silicone paints, alkali silicate paints, silica sol paints using colloidal silica, titanium oxide paints, ceramic paints, etc., organic, inorganic, organic / inorganic hybrid, etc. It may be a paint.
  • any of normal temperature hardening resin, thermosetting resin, or thermoplastic resin may be sufficient, and various normal temperature hardening resin, thermosetting resin, or thermoplastic resin is used individually or in mixture. be able to.
  • the coating material can be blended with additives such as a color pigment, a filler, a solvent, an ultraviolet absorber, an antioxidant, and a flow regulator as it is or as necessary.
  • the film thickness of the coating film formed on the surface of the aluminum shaped body is appropriately selected according to the purpose of use of the aluminum coating material, but the film thickness is usually 15 ⁇ m or more and 5 mm or less. Preferably, the thickness is 20 ⁇ m or more and 1000 ⁇ m or less. If the thickness is less than 15 ⁇ m, sufficient adhesion and corrosion resistance are not exhibited. Conversely, if the thickness is more than 5 mm, the durability does not change.
  • this coating film about the thickness of this coating film, the concave part of the aluminum shaped body and the fitting part of the coating film are more firmly locked and bonded to each other, so that the adhesion between the aluminum shaped body and the coating film is improved. This further improves the thickness of the coating film. Further, by increasing the thickness of the coating film, it is possible to more reliably prevent entry of impurities from the outside into the interface between the aluminum shaped body and the coating film and further improve the corrosion resistance. Furthermore, since the heat conductivity of the aluminum body can be lowered to provide heat insulation, it is possible to prevent condensation in building materials and the like, and to suppress extreme cold feeling in everyday items such as tables and chairs. .
  • the coating film formed on the surface of the aluminum shaped body may itself be a top coating film that forms the outermost layer surface of the aluminum coating material as described above, but a top coating film is further laminated thereon. Therefore, it may be a primer coating film that functions as a primer layer.
  • the film thickness of the primer coating that functions as the primer layer is usually the same. It should be 1 ⁇ m or more and 200 ⁇ m or less, preferably 5 ⁇ m or more and 150 ⁇ m or less. If the thickness is less than 1 ⁇ m, sufficient adhesion and corrosion resistance will not be exhibited. On the other hand, if the thickness is greater than 200 ⁇ m, the adhesion with the top coating film will not change. .
  • the top coating film is formed by further applying a top coating film on the coating film.
  • a top coating film there are no particular restrictions, for example, acrylic paint, polyester paint, urethane paint, acrylic urethane, acrylic polyester, epoxy paint, fluorine paint, alkyd paint, aminoalkyd paint, vinyl paint, chloride Examples include rubber paint, silicon paint, acrylic silicon paint, urethane silicon paint, acrylic urethane silicon paint, alkali silicate paint, silica sol paint using colloidal silica, titanium oxide paint, ceramic paint, etc. Organic, inorganic, organic / inorganic hybrid, etc. Any paint may be used.
  • the top coating film is not limited to a single layer coating film but may be a multilayer coating film having two or more layers. Further, although the film thickness is not particularly limited, it is usually preferably 5 ⁇ m or more and 5 mm or less.
  • the aluminum coating material of the present invention has extremely high adhesion and airtightness at the interface (aluminum / coating film interface) between the aluminum shaped body and the coating film, and excellent adhesion even when exposed to harsh environments. In addition, it can maintain airtightness and maintain excellent corrosion resistance, is chromium-free, has excellent durability, and can maintain high reliability over a long period of time.
  • the aluminum coating material of the present invention includes, for example, building interiors and exteriors, various building members such as building outer walls and interiors, road materials, various cabinets, refrigerated vehicle container interiors and exteriors, refrigerated showcases, automotive parts, electric / electronics It can be suitably used for aluminum coated products and aluminum bonded products in a wide range of fields such as parts, home appliances, and various daily necessities.
  • FIG. 1 is a cross-sectional schematic view for illustrating a concave portion by copying a cross section in the thickness direction of an aluminum shape according to the first embodiment.
  • FIG. 2 is a cross-sectional explanatory view showing a typical example of the shape of the concave portion conceived from FIG.
  • FIG. 3 is an explanatory cross-sectional view for explaining a method for observing and evaluating a coating film / aluminum / coating layer laminated portion in an aluminum coating material.
  • Example 1 [Preparation of aluminum shape] A 70 mm x 150 mm aluminum piece (aluminum alloy material) was cut out from a 0.7 mm thick aluminum alloy (JISA 1050-H24) plate, and the resulting aluminum piece was first immersed in a 30 wt% nitric acid aqueous solution at room temperature for 5 minutes. After that, rinse thoroughly with ion-exchanged water, then immerse in a 5 wt% sodium hydroxide solution at 50 ° C. for 1 minute, then rinse with water, and further immerse in a 30 wt% nitric acid aqueous solution at room temperature for 3 minutes and then perform pretreatment. did.
  • an etching solution (chlorine ion concentration: prepared by adding 54 g / L of aluminum chloride hexahydrate (AlCl 3 .6H 2 O) to a 2.5 wt% hydrochloric acid aqueous solution of the aluminum piece after the above pretreatment. 48g / L) is etched for 4 minutes at 66 ° C and then washed with water, further immersed in a 30wt% nitric acid aqueous solution for 3 minutes at room temperature, then washed with water, dried with hot air at 120 ° C for 5 minutes, and boiled water The aluminum shape body for making the evaluation sample of a test and a salt spray test was created.
  • the thickness direction of an aluminum shape body Determine the top line (TL) perpendicular to this thickness direction in the cross section and passing through the highest part of the uneven part, and then roughly the same as above, perpendicular to the thickness direction of the aluminum body and uneven Determine the bottom line (BL) that passes through the deepest part of the part, and draw a line segment in the direction perpendicular to the bottom line (BL) from the top line (TL), pass through the middle part of this line segment, And the distance between the gaps between the aluminum shape on the half line (HL) drawn parallel to the top line (TL) [or bottom line (BL)] Width (d) and the shape and size of the concave part formed due to the uneven part on the surface of the aluminum shape body (Aperture width and depth) were observed
  • the result of observing the cross section of an area with an aluminum shape with a scanning electron microscope is, for example, as shown in the cross section of FIG. 1 (1: aluminum shape, TL: top line, BL: bottom line, HL: half line) , And d: opening width), and a typical example of the shape of the concave portion 3 conceived from FIG. 1 is a snow candy from a part of the opening edge toward the center in the opening width direction as shown in FIG.
  • a concave portion having a protruding portion protruding in a shape shape a: see FIG.
  • the size (opening width and depth) of the concave portion observed in the cross section of the region where the aluminum body was measured and the ratio thereof were as follows: the concave portion having an opening width of 0.1 ⁇ m to 1 ⁇ m per 0.1 mm square. 10 to 100, 1 to 10 concave portions with an opening width of 1 ⁇ m to 10 ⁇ m, 1 to 3 concave portions with an opening width of 11 ⁇ m to 30 ⁇ m, and a depth within a range of 0.1 ⁇ m to 30 ⁇ m. there were.
  • the concave shape having an opening width of 0.1 ⁇ m to 1 ⁇ m per 0.1 mm square is substantially the same as described above. 10 to 50 parts, 1 to 50 concave parts with an opening width of 1 ⁇ m to 10 ⁇ m, 1 to 2 concave parts with an opening width of 11 ⁇ m to 30 ⁇ m, and a depth range of 0.1 ⁇ m to 20 ⁇ m It was in. The size of the concave portion was hardly changed even when the observation place was changed.
  • Example 2 An aluminum shaped body was produced in the same manner as in Example 1 except that JIS A1100-H14 was used as the aluminum alloy plate from which the aluminum piece was cut. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • Example 3 An aluminum shaped body was produced in the same manner as in Example 1 except that JIS A5052-H34 was used as the aluminum alloy plate from which the aluminum piece was cut. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • Example 4 In the same manner as in Example 1 above, except that an etching solution (chlorine ion concentration: 30 g / L) prepared by adding 50 g / L sodium chloride in a 50 wt% phosphoric acid aqueous solution was used for the etching treatment, an aluminum shape was used. The body was made. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • Example 5 An aluminum shaped body was obtained in the same manner as in Example 1 except that an etching solution (chlorine ion concentration: 30 g / L) prepared by adding 50 g / L sodium chloride in a 10 wt% sulfuric acid aqueous solution was used for the etching treatment. was made. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • chlorine ion concentration: 30 g / L chlorine ion concentration: 30 g / L
  • Example 6 In the same manner as in Example 1 above, except that an etching solution (chlorine ion concentration: 30 g / L) prepared by adding 50 g / L sodium chloride in a 30 wt% oxalic acid aqueous solution was used for the etching treatment, an aluminum shape was used. The body was made. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • Example 7 to 10 and 17 An aluminum shaped body was produced in the same manner as in Example 1 above. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • Example 11 Except for using an etching solution (chlorine ion concentration: 54 g / L) prepared by adding 50 g / L sodium chloride (NaCl) in a 2.5 wt% hydrochloric acid aqueous solution, the same as in Example 1 above. Thus, an aluminum shape body was produced. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • chlorine ion concentration: 54 g / L prepared by adding 50 g / L sodium chloride (NaCl) in a 2.5 wt% hydrochloric acid aqueous solution
  • Example 12 An aluminum shaped body was used in the same manner as in Example 1 except that a 2.5 wt% hydrochloric acid aqueous solution (chlorine ion concentration: 24 g / L) was used as the etching solution, and the substrate was washed with water after being immersed at 76 ° C. for 10 minutes. Was made. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • Examples 13 to 16 Immerse for 10 minutes at 30 ° C using an etching solution (chlorine ion concentration: 173 g / L) prepared by adding 268 g / L of aluminum chloride hexahydrate (AlCl 3 ⁇ 6H 2 O) in 6 wt% hydrochloric acid solution After that, an aluminum shaped body was produced in the same manner as in Example 1 except that an etching process was performed for washing with water. About the obtained aluminum shape body, it carried out similarly to the case of the said Example 1, and observed the concave part, evaluated the shape and magnitude
  • Examples 6 to 9 The aluminum shapes of Examples 6 to 9 obtained above were pretreated by the following method in advance before coating to prepare an aluminum coating material. That is, in Examples 6 and 8, a 2 wt% aqueous solution of a degreasing agent containing sodium metasilicate (degreasing agent A: trade name manufactured by Nippon Paint Co., Ltd .: Surf Cleaner 155) was used as the alkaline solution containing the silicon compound. After dipping at 60 ° C. for 30 seconds, it was washed with water and dried at 50 ° C. for 5 minutes.
  • a degreasing agent A trade name manufactured by Nippon Paint Co., Ltd .: Surf Cleaner 155
  • Example 7 0.2 wt% -phosphoric acid aqueous solution containing 2% by weight of colloidal silica (trade name: Snowtex-O manufactured by Nissan Chemical Industries, Ltd.) was coated with a bar coater # 3 at 100 ° C. Dry for 1 minute.
  • colloidal silica trade name: Snowtex-O manufactured by Nissan Chemical Industries, Ltd.
  • Example 1 [Preparation of aluminum coating material] [Examples 1, 5 and 13]
  • the paint A shown in Table 3 below was spray-coated, baked at PMT 170 ° C. for 20 minutes, and dried to form a coating film having the thickness shown in Table 1.
  • Aluminum paints 5 and 13 were prepared.
  • Example 2 [Examples 2, 3 and 4]
  • the coating material B shown in Table 3 below was applied as a primer by bar coating, dried at a maximum reached temperature (PMT: Peak metal temperature) of 210 ° C. for 40 seconds and dried. A coating film having a thickness of 1 was formed.
  • the coating material C shown in Table 3 below was bar-coated, baked at PMT 225 ° C. for 60 seconds and dried to form a coating film having the thickness shown in Table 1, Examples 2, 3 and 4 An aluminum coating material was prepared.
  • Example 6 In Example 6, the coating material D shown in Table 3 below was bar-coated, dried at a maximum temperature (PMT) of 220 ° C. for 60 seconds, and a coating film having a film thickness shown in Table 1 was formed. Then, the aluminum coating material of Example 6 was prepared.
  • PMT maximum temperature
  • Example 7 In Example 7, the coating material D shown in Table 3 below was bar-coated, baked at 180 ° C. for 20 minutes, and dried to form a coating film having the film thickness shown in Table 1. An aluminum coating material was prepared.
  • Example 8 and 9 In Examples 8 and 9, the coating material E shown in Table 3 below was spray-coated as a primer, baked at 150 ° C. for 10 minutes and dried to form a coating film having the thickness shown in Table 1, and then The paint F shown in Table 3 was spray-coated, baked at 200 ° C. for 30 minutes and dried to form a coating film having the thickness shown in Table 1, and aluminum coating materials of Examples 8 and 9 were prepared. .
  • Example 10 In Example 10, the coating material G shown in Table 3 below was electrostatically powder coated and baked at 170 ° C. for 20 minutes to form a coating film having the film thickness shown in Table 1. Prepared.
  • Examples 11, 12, and 14 In Examples 11, 12, and 14, the paint H shown in Table 3 below was spray-coated as a primer, baked at 120 ° C. for 10 minutes and dried to form a coating film having the thickness shown in Table 1, The coating material I shown in Table 3 below is electrostatically powder coated and baked at 180 ° C. for 20 minutes to form a coating film having the film thickness shown in Table 1 to prepare the aluminum coating materials of Examples 11, 12 and 14. did.
  • Example 15 16 and 17 In Examples 15, 16 and 17, the coating material J shown in Table 3 below was applied as an electrostatic powder, and baked at 170 ° C. for 20 minutes and dried to form a coating film having the thickness shown in Table 1. Then, the coating material F shown in Table 3 below is spray-coated and baked at 180 ° C. for 20 minutes to form a coating film having the film thickness shown in Table 1 to prepare the aluminum coating materials of Examples 15, 16 and 17. did.
  • Salt spray test A salt spray test was performed on the aluminum coating materials of Examples 1 to 17. The salt spray test was carried out for 1000 hours with a cross cut made according to the method of JIS K5600. The coating after 1000 hours has no corrosion, blistering, etc. in the cut part, and the cut part has good adhesion, and the cut part has corrosion of 1 mm or less, no blistering, and good adhesion. The evaluation was evaluated as “Good”, and “X” when the corrosion of the cut portion was 1 mm or more, or the occurrence of blistering or poor adhesion was observed. The results are shown in Table 1.
  • Comparative Example 1 Using the aluminum piece (aluminum alloy material) of Example 1, the aluminum shape body of Comparative Example 1 was prepared without performing an etching treatment only by pre-treatment. Subsequently, the coating material A shown in Table 3 below was spray-coated, baked at PMT 170 ° C. for 20 minutes, and dried to form a coating film having a film thickness shown in Table 2. Thus, an aluminum coating material of Comparative Example 1 was prepared.
  • Example 2 After pretreatment using the aluminum piece (aluminum alloy material) of Example 1, it was immersed in 2.5 wt% hydrochloric acid aqueous solution for 4 minutes at 66 ° C. and washed with water, and 5 wt% sodium hydroxide solution at 50 ° C. for 5 minutes.
  • the aluminum shape was prepared by immersing in water for 30 minutes, further immersing in 30 wt% nitric acid at room temperature for 3 minutes, washing with water, and then drying with hot air at 120 ° C. for 5 minutes.
  • paint B shown in Table 3 below was applied as a primer by bar coating, dried at a maximum reached temperature (PMT: Peak metal temperature) of 210 ° C.
  • Example 4 After pretreatment using the aluminum piece (aluminum alloy material) of Example 1, it was immersed in a 10 wt% sulfuric acid aqueous solution at 66 ° C. for 4 minutes and washed with water, and then dried with hot air at 120 ° C. for 5 minutes to form an aluminum shape. The body was prepared. Next, the coating material D shown in Table 3 below was bar-coated, and was baked at 180 ° C. for 20 minutes and dried to form a coating film having the film thickness shown in Table 2. The aluminum coating material of Comparative Example 3 was prepared.
  • Comparative Example 5 After pretreatment using the aluminum piece (aluminum alloy material) of Example 1, it was immersed in a 30 wt% oxalic acid aqueous solution at 66 ° C. for 4 minutes, washed with water, and then dried with hot air at 120 ° C. for 5 minutes to obtain aluminum. Shaped bodies were prepared. Subsequently, the coating material G shown in Table 3 below was electrostatically powder coated and baked at 170 ° C. for 20 minutes to form a coating film having a film thickness shown in Table 2. Thus, an aluminum coating material of Comparative Example 5 was prepared.
  • Comparative Example 7 After pretreatment using the aluminum piece (aluminum alloy material) of Example 1, it was immersed in an etching solution composed of a 30 wt% nitric acid aqueous solution at 66 ° C. for 4 minutes, washed with water, and then dried with hot air at 120 ° C. for 5 minutes. Thus, an aluminum shape was prepared. Subsequently, the coating material F shown in Table 3 below was spray-coated and baked at 180 ° C. for 20 minutes to form a coating film having a film thickness shown in Table 2. Thus, an aluminum coating material of Comparative Example 7 was prepared.
  • Comparative Example 8 Using the aluminum piece (aluminum alloy material) of Example 1 and performing air blasting using # 150 alumina having an average particle diameter of 100 ⁇ m, the pretreatment of Example 1 is performed, and the aluminum body is formed without performing the etching process. Prepared. Subsequently, the coating material F shown in Table 3 below was spray-coated and baked at 180 ° C. for 20 minutes to form a coating film having a film thickness shown in Table 2. Thus, an aluminum coating material of Comparative Example 8 was prepared.
  • Example 9 The aluminum piece (aluminum alloy material) of Example 1 was pretreated and then anodized by the sulfuric acid method to provide an anodized film layer on the entire surface of each test piece.
  • This anodizing treatment is performed by electrolysis under a condition of a current density of 1.5 A / m 2 using an electrolytic solution of 160 g / L sulfuric acid at 23 ° C., and forming an anodized film having a thickness of 7 ⁇ m to form an aluminum body Was prepared.
  • paint A shown in Table 3 below was sprayed and baked at 170 ° C. for 20 minutes.
  • a coating film having the film thickness shown was formed, and an aluminum coating material of Comparative Example 9 was prepared.
  • Example 10 After pre-treatment using the aluminum piece (aluminum alloy material) of Example 1, shot blast treatment is performed using alumina particles having a particle size of 150 ⁇ m, and the surface roughness Rz (Rz: JIS B 0601-1994) is complied with. A roughened surface having a 10-point average roughness) of 40 ⁇ m was formed. Next, an aluminum shaped body was prepared by forming an anodic oxide film having a thickness of 20 ⁇ m by electrolysis under a condition of a current density of 1.5 A / m 2 using an electrolyte at 23 ° C. with 160 g / L of sulfuric acid. Then, after washing with pure water at 82 ° C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • ing And Chemical Polishing (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne un matériau en aluminium revêtu qui comprend un objet en aluminium façonné constitué d'aluminium ou d'un alliage d'aluminium et d'un revêtement exempt de chrome et qui présente une adhésion interfaciale extrêmement élevée et une grande étanchéité aux gaz entre l'objet en aluminium façonné et le revêtement, qui conserve une excellente résistance à la corrosion même dans des environnements rigoureux, et qui peut présenter une excellente durabilité. L'invention concerne aussi un procédé de fabrication du matériau en aluminium revêtu. Le matériau en aluminium revêtu est constitué par : un objet en aluminium façonné qui est constitué d'un alliage d'aluminium et qui a une pluralité de creux dus à des irrégularités formées dans la surface ; et par un revêtement qui a des parties de remplissage formées par pénétration d'un matériau de revêtement dans les creux et solidification subséquente. Du fait de l'action des creux et des parties de remplissage, l'objet en aluminium façonné et le revêtement ont été engagés l'un dans l'autre.
PCT/JP2010/072109 2009-12-11 2010-12-09 Matériau en aluminium revêtu et procédé pour sa fabrication WO2011071105A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009281866A JP2011121307A (ja) 2009-12-11 2009-12-11 アルミニウム塗装材及びその製造方法
JP2009-281866 2009-12-11

Publications (1)

Publication Number Publication Date
WO2011071105A1 true WO2011071105A1 (fr) 2011-06-16

Family

ID=44145650

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/072109 WO2011071105A1 (fr) 2009-12-11 2010-12-09 Matériau en aluminium revêtu et procédé pour sa fabrication

Country Status (3)

Country Link
JP (1) JP2011121307A (fr)
TW (1) TW201137174A (fr)
WO (1) WO2011071105A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014170946A1 (fr) * 2013-04-15 2014-10-23 日本軽金属株式会社 PROCÉDÉ DE FABRICATION D'UN ÉLÉMENT D'ALLIAGE D'ALUMINIUM DE TYPE Al-Mg-Si POUR LIAISON À LA RÉSINE ET ÉLÉMENT D'ALLIAGE D'ALUMINIUM POUR LIAISON À LA RÉSINE AINSI OBTENU
CN104148258B (zh) * 2014-07-21 2016-09-21 浙江德清森朗装饰材料有限公司 一种氟碳铝单板的制造工艺

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5640466A (en) * 1979-09-11 1981-04-16 Toshiba Electric Appliance Co Ltd Coating method of fluorine resin
JPS6323771A (ja) * 1986-07-17 1988-02-01 Toshiba Corp 流動浸漬絶縁方法
JPH03224666A (ja) * 1990-01-31 1991-10-03 Sumitomo Electric Ind Ltd 弗素樹脂被覆法
JP2003321784A (ja) * 2002-04-26 2003-11-14 Asahi Denka Kogyo Kk アルミニウム含有材料用表面処理液及びアルミニウム含有材料の表面処理方法
JP2006274437A (ja) * 2005-03-30 2006-10-12 Neos Co Ltd アルミニウムおよびアルミニウム合金の粗面化処理方法
JP2007138224A (ja) * 2005-11-16 2007-06-07 Kanto Gakuin Univ Surface Engineering Research Institute アルミニウム材又はアルミニウム合金材の表面加工方法及び該方法により加工された表面を有するアルミニウム材又はアルミニウム合金材
JP2008140904A (ja) * 2006-11-30 2008-06-19 Nichicon Corp 電解コンデンサ用アルミニウム電極箔の製造方法
JP2008144195A (ja) * 2006-12-07 2008-06-26 Sankyo Tateyama Aluminium Inc アルミニウム材の表面処理方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3916203B2 (ja) * 2000-06-06 2007-05-16 メック株式会社 アルミニウムまたはアルミニウム合金の表面粗化剤およびそれを用いる表面粗化法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5640466A (en) * 1979-09-11 1981-04-16 Toshiba Electric Appliance Co Ltd Coating method of fluorine resin
JPS6323771A (ja) * 1986-07-17 1988-02-01 Toshiba Corp 流動浸漬絶縁方法
JPH03224666A (ja) * 1990-01-31 1991-10-03 Sumitomo Electric Ind Ltd 弗素樹脂被覆法
JP2003321784A (ja) * 2002-04-26 2003-11-14 Asahi Denka Kogyo Kk アルミニウム含有材料用表面処理液及びアルミニウム含有材料の表面処理方法
JP2006274437A (ja) * 2005-03-30 2006-10-12 Neos Co Ltd アルミニウムおよびアルミニウム合金の粗面化処理方法
JP2007138224A (ja) * 2005-11-16 2007-06-07 Kanto Gakuin Univ Surface Engineering Research Institute アルミニウム材又はアルミニウム合金材の表面加工方法及び該方法により加工された表面を有するアルミニウム材又はアルミニウム合金材
JP2008140904A (ja) * 2006-11-30 2008-06-19 Nichicon Corp 電解コンデンサ用アルミニウム電極箔の製造方法
JP2008144195A (ja) * 2006-12-07 2008-06-26 Sankyo Tateyama Aluminium Inc アルミニウム材の表面処理方法

Also Published As

Publication number Publication date
TW201137174A (en) 2011-11-01
JP2011121307A (ja) 2011-06-23

Similar Documents

Publication Publication Date Title
JP5581680B2 (ja) 耐候性に優れたアルミ・樹脂複合品及びその製造方法
EP2265441B1 (fr) Revêtement protecteur pour métaux
EP1874980B1 (fr) Procede de formation d'une couche de conversion sans chromate, bien visible, pour magnesium et alliages de magnesium
CA2585283A1 (fr) Procede de recouvrement anodique de l'aluminium et/ou du titane avec des oxydes ceramiques
WO2007061011A1 (fr) Plaque metallique enduite d'une couche de conversion chimique et son procede de fabrication
WO2011071062A1 (fr) Composite d'aluminium lie et son procede de fabrication
TWI678433B (zh) 鋅或鋅合金基材用３價鉻化成處理液及使用該處理液的化成處理方法
ES2646760T3 (es) Agente de tratamiento de conversión química para el tratamiento superficial de un sustrato metálico y método de tratamiento superficial del sustrato metálico utilizando el mismo
JP2010538158A (ja) 耐食性アルミニウム合金基材及びその製造方法
WO2012143934A2 (fr) Formulation de passivation anticorrosion et son procédé de préparation thereof
JP6369745B2 (ja) 陽極酸化皮膜及びその封孔処理方法
WO2011071105A1 (fr) Matériau en aluminium revêtu et procédé pour sa fabrication
JP6441655B2 (ja) 下地処理液、下地処理液を用いた有機被覆亜鉛めっき鋼管の製造方法、及び、有機被覆亜鉛めっき鋼管
EP3239355B1 (fr) Liquide de conversion chimique à base de chrome trivalent pour bases de zinc ou d'alliage de zinc
JP4414745B2 (ja) 耐食性に優れ、環境負荷の小さい塗装金属板
JP3105322B2 (ja) 光輝性アルミホイールの無色クロメート皮膜形成方法
JP5125284B2 (ja) アルミニウム塗装材及びその製造方法
JP4522615B2 (ja) 表面処理アルミニウム材及びアルミニウム成形体
JP6695767B2 (ja) アルミニウム塗装材の製造方法
JP4176581B2 (ja) 表面処理アルミニウム材及びアルミニウム成形体
WO2009093545A1 (fr) Produit en acier revêtu
JP4103861B2 (ja) 黒色化鋼板及びその製造方法
JP5728740B2 (ja) 化成皮膜の仕上げ剤及び仕上げ処理方法
Lampman Chemical Conversion Coatings
JP3156495B2 (ja) 無塗装ＡｌまたはＡｌ合金部材

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10836025

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10836025

Country of ref document: EP

Kind code of ref document: A1