WO2015129660A1 - Article coloré façonné en aluminium et son procédé de fabrication - Google Patents

Article coloré façonné en aluminium et son procédé de fabrication Download PDF

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Publication number
WO2015129660A1
WO2015129660A1 PCT/JP2015/055146 JP2015055146W WO2015129660A1 WO 2015129660 A1 WO2015129660 A1 WO 2015129660A1 JP 2015055146 W JP2015055146 W JP 2015055146W WO 2015129660 A1 WO2015129660 A1 WO 2015129660A1
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WIPO (PCT)
Prior art keywords
pigment
molded body
pores
aluminum
aluminum molded
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PCT/JP2015/055146
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English (en)
Japanese (ja)
Inventor
博義 山本
伊藤　淳
伊藤　征司郎
Original Assignee
株式会社サクラクレパス
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Application filed by 株式会社サクラクレパス filed Critical 株式会社サクラクレパス
Priority to US15/121,280 priority Critical patent/US20160362808A1/en
Priority to JP2016505220A priority patent/JP6720073B2/ja
Priority to CN201580010252.5A priority patent/CN106068338A/zh
Publication of WO2015129660A1 publication Critical patent/WO2015129660A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment
    • C25D11/22—Electrolytic after-treatment for colouring layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/10—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing organic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/12—Anodising more than once, e.g. in different baths

Definitions

  • the present invention relates to a colored aluminum molded body and a method for producing the same. .
  • the aluminum molded body itself has a metallic luster derived from metallic aluminum, and when such a molded body is used for various colored applications, it is necessary to perform well-known surface treatment as necessary, and then perform black processing. It was painted using a colored paint of any desired color such as red, white, etc.
  • a colored paint of any desired color such as red, white, etc.
  • a mixed liquid containing titanyl sulfate and the like and a complexing agent that forms a cation is used.
  • a titanyl electrolysis process for forming a titanium dioxide-containing film by depositing titanium dioxide on the surface of the anodized film and the inner surface of the hole by electrolytic treatment There is known a method of forming a photocatalytic film made of titanium dioxide on the surface of the anodized film and the inner surface of the hole, which has a baking treatment step of changing to a photocatalytic film made of titanium.
  • Patent Document 2 semiconductor fine particles such as titanium oxide having an average particle diameter of 1 nm to 1000 nm having a photocatalytic action are aggregated and deposited on an anodized film formed on a substrate surface made of aluminum or an aluminum alloy.
  • An aluminum or aluminum alloy material characterized by being coated with a photocatalytic film is described, and there is a titanium oxide film formed outside the pores, not inside the pores formed in the anodized film.
  • Patent Document 3 discloses that an aluminum material anodized at a high voltage is subjected to electrolytic coloring by applying an AC voltage in a metal salt solution
  • Patent Document 4 includes an aluminum material on which an anodized film is formed. Etching with a dilute alkaline aqueous solution to chemically dissolve the exposed surface of the barrier layer at the bottom of the pores of the anodized film, followed by electrolytic coloring and electrophoretic coloring in an electrolytic coloring bath containing pigment particles or metal salts It is described to do.
  • Japanese Patent No. 4905659 Japanese Patent No. 3326071 Japanese Patent Laid-Open No. 11-335893 Japanese Patent Laid-Open No. 11-236697
  • the white coating film was peeled off, and the appearance was sometimes impaired.
  • the diameter of the pores must be increased so that the pigment can be filled in such an amount that the coloring power can be exerted. Then, the surface of the aluminum molded body becomes rough, and there is a possibility that the aesthetic appearance may be impaired.
  • the colored film obtained in this way is not a dense film, but has a large pore diameter, so that the aluminum molded body has already had a certain amount of light due to reflection of light by the pores before filling with titanium oxide.
  • a method comprising a titanyl electrolytic treatment step of forming titanium dioxide film by depositing titanium dioxide on the surface of the anodized film and the inner surface of the hole as described in Patent Document 1, and a step of firing the titanium dioxide film
  • a titanyl electrolytic treatment step of forming titanium dioxide film by depositing titanium dioxide on the surface of the anodized film and the inner surface of the hole as described in Patent Document 1
  • a step of firing the titanium dioxide film According to the above, it is difficult to deposit a sufficient amount of titanium dioxide for photocatalyst, and an aluminum molded body that is relatively inferior in heat resistance is heated to a high temperature, so that the molded body may be deformed or properties may be altered. was there.
  • an anodized aluminum plate is immersed in a titanium oxide sol and subjected to electrophoresis, so that titanium oxide particles are not formed in the pores formed on the surface of the aluminum plate but on the surface.
  • the photocatalyst is supported by precipitating, but the supported titanium oxide is for the photocatalyst and is not in the pores, and the amount carried in the pores is small.
  • the method described in Patent Document 3 is a method of coloring an aluminum material surface provided with an anodized film by applying an AC voltage in a metal salt solution, but the anodizing treatment is performed only once, and There is no suggestion of depositing a metal compound in the pores.
  • Patent Document 4 describes a method of filling a pigment into pores formed by an anodized film, the barrier layer is dissolved by etching the anodized film before filling the pigment.
  • this etching step cannot naturally dissolve only the barrier layer in the pores, but also etches the entire anodized film.
  • a surface having unevenness is formed on the entire anodized film, and even if the surface can be colored, the aluminum plate only forms an uneven surface with unevenness.
  • this anodized film disappears by etching the once formed anodized film. Therefore, although there are pores, the pores are not protected by the anodized film, and the inside of the pores and the aluminum material surface corrode as the aluminum material is used. Therefore, the present invention fills the pores formed by anodization with pigment particles such as titanium dioxide, has an opaque and sufficient colored film, maintains the original shape, and maintains the original physical properties by the anodized film. It is to obtain an aluminum molded body provided.
  • the aluminum molded body according to 1 or 2 wherein a length of the pore molded body in the depth direction is 5 to 50 ⁇ m. 4).
  • An aluminum molded body is subjected to an anodizing treatment step including an anodizing treatment step under a condition where the current value is constant and an anodizing treatment step followed by a constant voltage value, and a pigment is formed in the formed pores.
  • the method for coloring the surface of an aluminum molded article according to 5, wherein the treatment for filling the pigment is a treatment for electrophoresis using a pigment dispersion and / or a pigment sol-containing solution.
  • the colored film does not fall off as long as the anodized film does not peel off, as compared with the conventional coating method.
  • a larger amount of pigment can be fixed in the colored aluminum molded body in which the pigment is put in the pores of the anodized film, a particularly deep color can be stably exhibited.
  • secondary aggregation can be performed in the pores, sufficient pigmentation can be achieved even when a pigment having a small primary particle diameter and not exhibiting coloration as a pigment is used.
  • the present invention can be carried out by filling the fine particles formed in the anodic oxide film with pigment particles dispersed in a solvent. Further, even if the particle size is smaller, for example, particles of titanium oxide or the like that originally do not exhibit white color because the primary particles are small, using a dispersion in which the sol-like particles are dispersed, As a result of the aggregated state of these pigment sols, the light incident from the outside is diffusely reflected between the titanium oxide particles constituting the aggregated particles, resulting in high opacity. The aggregated titanium oxide particles can exhibit a white color, and as a result, the anodized film can exhibit a white color. The same applies to other pigments as well as titanium oxide.
  • the opening of the pores of the anodized film is sufficiently large, and for example, titanium oxide particles or other pigments already having coloring ability as white pigments, or aggregated particles thereof are introduced from the openings, and as a result In the case of exhibiting a white color, a denser and more colored anodic oxide film can be obtained as compared with the aluminum molded body.
  • Such an aluminum molded body of the present invention is produced by the following two-step anodic oxidation pore formation step and subsequent pigment filling step. The matter common to this method is to introduce a pigment or sol into the pores obtained by anodizing treatment of an aluminum molded body that is an object to be treated.
  • the anodizing method used in the present invention is a method performed on a molded body made of the following aluminum material (aluminum material of an aluminum molded body).
  • the aluminum material constituting the aluminum molded body of the present invention may be a material made of only aluminum, but is generally a material called an aluminum alloy (for example, Al—Mn alloy, Al—Mg alloy, Al—Mg—Si alloy). Or any other material that can be anodized to form pores.
  • the aluminum material itself may be an already colored material by being alloyed with another metal. Which aluminum material is used is determined by the use of the aluminum molded body of the present invention.
  • the pigment that can be used in the present invention may be a known pigment, such as titanium oxide, iron oxide, carbon black, zinc oxide, copper phthalocyanine blue, copper phthalocyanine green, azo, quinacridone, anthraquinone, diketopyrrolopyrrole.
  • Perylene-based, perinone-based, dioxazine-based compounds or derivatives thereof can be used, and pigments that can be contained in the treatment liquid in the anodizing treatment step can be selected.
  • a particle diameter the thing of the well-known particle diameter of the range which can be used as a color pigment can be employ
  • a sol made of a material that can be used as the pigment can be adopted.
  • the first stage anodizing treatment performed to obtain the aluminum molded body of the present invention is a treatment generally performed on the surface of the aluminum molded body to impart corrosion resistance and decorativeness to the surface. It is necessary that the process be capable of forming holes.
  • An aluminum molded body is brought into electrical contact with the anode of the anodizing apparatus, immersed in an electrolytic solution together with the anode and the cathode, and energized between the anode and the cathode, whereby an anodized film is formed on the aluminum molded body.
  • an electrolytic solution containing an organic acid containing phosphoric acid such as an oxalic acid / phosphoric acid mixture, a malonic acid / phosphoric acid mixture, a maleic acid / phosphoric acid mixture, or the like is preferably used.
  • an organic acid containing phosphoric acid such as an oxalic acid / phosphoric acid mixture, a malonic acid / phosphoric acid mixture, a maleic acid / phosphoric acid mixture, or the like.
  • the present invention is not limited to these.
  • maleic acid / phosphoric acid mixtures are preferred, for example.
  • the first stage of anodic oxidation is performed under the condition that the current density is kept constant.
  • the current density at this time is preferably 0.5 to 2.0 A / dm 2 .
  • the generated pores are formed as pores 3 that are long columnar spaces extending in the depth direction of the anodized film 2 formed on the surface of the aluminum molded body 1, for example, as shown in FIG.
  • the diameter of the opening can be arbitrarily adjusted according to the anodic oxidation conditions.
  • the pore of the anodized film formed by this step has a diameter of 50 to 300 nm.
  • the thickness is preferably 100 to 250 nm. If it is larger than 300 nm, it is difficult to make the anodized film uniform, and if it is less than 50 nm, it becomes difficult to deposit a sufficient amount of pigment particles such as titanium oxide particles inside the pores.
  • the length of the pores is not particularly limited, but is 5 to 50 ⁇ m from the aluminum surface in the thickness direction in order to deposit an amount of the pigment necessary to be sufficiently colored by the pigment, preferably 10 to 40 ⁇ m.
  • the anodic oxidation treatment is performed by changing the applied voltage.
  • the process is performed by decreasing the voltage step by step every predetermined time and / or every time until a predetermined current value is reached.
  • the current value becomes once almost 0, then gradually the current value increases, and eventually the current value in the steady state commensurate with E 2 become. That is, the thickness of the barrier layer is proportional to the voltage. Even immediately after change to E 2 a current value is 0, the barrier layer is thin to the barrier layer is dissolved in the electrolyte solution, finally to progress electrolytic reaction becomes current value in the steady state.
  • the treatment liquid in these steps may also be a known treatment liquid for anodizing treatment that can be used in the first stage anodizing treatment, and the electrolytic solution used in the first stage can be used continuously.
  • the step of depositing the pigment in the pores of the anodized film in the method of the present invention is a step of causing the pigment dispersion and / or the pigment sol to be electrophoresed on the aluminum molded body after the anodizing treatment.
  • the pigment dispersion used here contains a predetermined pigment and a pigment-dispersing resin, and optionally a water-soluble organic solvent, in an aqueous solvent, and if necessary, a known additive may be used in combination. Can do.
  • the concentration of the pigment in the pigment dispersion is in the range of 0.1 to 10.0% by weight, and if it deviates from these ranges, the pigment may be insufficiently filled or the dispersibility may deteriorate.
  • a titanium oxide dispersion when used, its pH is 8.0 or more, preferably 9.0 to 11.0.
  • the pigment is preferably composed of primary particles or secondary particles.
  • the average particle diameter (D50) is preferably 5 to 100 nm. When the average particle diameter exceeds 100 nm, it becomes difficult to enter the pores from the openings of the pores formed in the anodized film, and when the primary particle diameter is less than 5 nm, it is difficult to obtain.
  • Water-soluble resins that are dispersants and the like contained in the pigment dispersion include polyvinyl alcohol resins, gelatin, polyethylene oxide, polyvinyl pyrrolidone, acrylic resins, styrene-acrylic resins, acrylamide resins, urethane resins, dextrans. , Dextrin, carrageenan ( ⁇ , ⁇ , ⁇ , etc.), agar, pullulan, water-soluble polyvinyl butyral, hydroxyethyl cellulose, carboxymethyl cellulose, epoxy resin, polyimide resin, polyamide resin, cellulose resin, polyester resin, etc. It can be illustrated.
  • the content of the water-soluble resin is preferably 1 to 30% by weight when the entire dispersion liquid in which the pigment is dispersed is 100% by weight. In the method using the pigment sol, it is not always necessary to use the water-soluble resin.
  • water-soluble organic solvent contained in the dispersion examples include alcohols (for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol).
  • alcohols for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol).
  • polyhydric alcohols for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.
  • Polyhydric alcohol ethers for example, ethylene glycol monomethyl ether, ethylene glycol Ethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol Ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, etc.), amines (eg, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, triethylamine) , Morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylenetetramine, tetramine,
  • Preferable water-soluble organic solvents include polyhydric alcohols such as ethylene glycol. Furthermore, you may use a polyhydric alcohol and a polyhydric alcohol ether together.
  • the content of the water-soluble organic solvent is preferably 0 to 40% by weight when the dispersion obtained by dispersing the pigment is 100% by weight.
  • a known inorganic compound sol capable of obtaining an aluminum molded body which is aggregated to become a pigment and colored can be used.
  • a sol for example, a sol of an inorganic compound that can be a pigment such as a colloidal titanium oxide sol, a zinc oxide sol, an iron oxide sol, or a copper oxide sol can be used.
  • the pigment sol particles particles of about 5 to 100 nm can be employed.
  • Electrophoresis conditions using a pigment dispersion or pigment sol include an aluminum molded body in which pores are formed in a room temperature dispersion or sol, and the voltage is increased at a rate of 0.5 to 2 V per second. Maintain at ⁇ 200V for 30 seconds to 5 minutes.
  • the aluminum molded body is neutralized and the dispersion in the pores is further immersed by immersing in an aqueous solution of weak acid such as maleic acid such as 0.1 to 2.0% by weight at 20 to 70 ° C. for 1 to 10 minutes. Can also be fixed.
  • weak acid such as maleic acid
  • the pigment may adhere to the non-pore portions on the surface of the aluminum molded body.
  • the pigment adhering to the outside of the pores can be removed by washing with triethanolamine or water. Such removal eliminates the possibility of so-called covering and the difficulty of vivid coloring.
  • the aluminum molded body formed according to the present invention has a range of 2 to 30 mg / dm 2 as the metal when the pigment filled in the pores per 1 dm 2 (square decimeter) of the surface is a metal compound. It is.
  • the coloring power can be further improved as compared with the coloring by the conventional method.
  • the color of the surface has an L * value of 78 or more, and the a * and b * values are in the range of 0 ⁇ 5, respectively.
  • the aluminum molded body of the present invention may or may not be matt.
  • Such an aluminum molded body of the present invention can be used in many fields and applications where an aluminum molded body has been used. For example, in all uses such as furniture, tableware, containers, home appliances, daily necessities, etc., it can be adopted when a molded aluminum body having a white surface is required.
  • Example 1 Metal plate anodizing process
  • the anodizing treatment step was performed by the following first anodizing treatment (constant current anodizing treatment) and second anodizing treatment (constant voltage anodizing treatment).
  • first anodizing treatment An electrolytic solution for forming an anodic oxide film containing 30 g of 85% phosphoric acid and 30 g of maleic acid in 1 liter was prepared.
  • the electrolytic solution for forming the anodic oxide film was set at 30 ° C., and an aluminum plate was immersed therein, and anodized with a current density of 1.0 A ⁇ dm ⁇ 2 and an electrolysis time of 45 minutes. At this time, the final voltage of this anodizing process was about 120V. (Second anodizing treatment) Subsequently, the step of anodizing with the voltage kept constant as the second anodizing treatment step was performed while successively reducing the constant voltage. First, the voltage was lowered from 120V to 100V and fixed. Initially, the current value is low, but when the current value gradually increases and becomes a substantially constant current value, the voltage is then reduced to 80V, and similarly the voltage is fixed at 80V.
  • pigment dispersion and electrophoresis process As titanium oxide, 10 parts by weight of anatase-type titanium oxide powder having an average primary particle size of 6 nm determined by a transmission electron microscope is used, and BASF Jonkrill 679 (acrylic copolymer) is used as a dispersant. A pigment dispersion was prepared by dispersing 10 parts by weight in a solvent composed of triethanolamine and water. This dispersion contains 0.6% by weight of the titanium oxide having a particle size (D50% by volume based on dynamic light scattering measurement) of 28 nm, further containing triethanolamine, and having a pH of 8.3. Or it was prepared to 9.5.
  • the first anodized aluminum plate was subjected to a second anodizing treatment under the conditions shown in Table 1 below, followed by an electrophoresis step in the pigment dispersion.
  • the treated aluminum plate thus obtained was washed with a triethanolamine aqueous solution to remove the titanium oxide adhering to the outside of the pores, thereby eliminating the covering.
  • the method for measuring the amount of titanium per square decimeter of the surface shown in Table 1 and Table 2 is as follows. 50 ml of a solution prepared by mixing and dissolving 35 ml of 85% phosphoric acid and 20 g of chromic anhydride in 1 L of ion exchange water is prepared, and an aluminum plate that has been subjected to electrophoresis treatment of 20 mm ⁇ 30 mm is immersed in this solution. Dissolve the film at ⁇ 100 ° C. At this time, the dissolved film component and some titanium oxide particles present in the film component are present in the solution. Therefore, an appropriate amount (about 10 ml) of concentrated sulfuric acid is further added and heated to dissolve the titanium oxide.
  • This solution was prepared so that the total amount was 100 ml, and the amount of titanium in the solution was quantified by ICP-AES (inductively coupled plasma emission spectrometer).
  • L *, a *, and b * shown in Table 1 and Table 2 below are measured using a spectrophotometer SE2000 model manufactured by Nippon Denshoku Industries Co., Ltd., and the presence or absence of interference is processed aluminum plate Were visually inspected for the presence of interference colors.
  • the surface-treated aluminum plate corresponding to the present invention is three examples in the table having lightness L * of 82.15 or more. Is hardly seen. Further, the a * value is ⁇ 1.00 or more, and the b * value of those examples is ⁇ 3.60 or more. In addition, since these color characteristics are also influenced by the color of the aluminum plate which is a base material, these ranges are limited to this example. These three examples are all based on the fact that the final voltage of the second anodizing treatment is 40V or 60V, and the barrier layer is a thin film.
  • the graph shown in FIG. 2 shows the electrophoresis at the time of electrophoresis for each of the treatment conditions at the time of the second anodizing treatment for the colored aluminum plate obtained by filling the pigment into the pores by causing the pigment to migrate.
  • This explains the difference in conditions. 2 in FIG. 2 is when the second anodizing treatment is not performed and the pH of the pigment during electrophoresis is 8.3, which is outside the scope of the present invention.
  • the graph indicated by 2 is subjected to the second anodizing treatment at 40V15 minutes
  • the dispersion at the time of electrophoresis is pH 8.3
  • the graph indicated by 3 is subjected to the second anodizing treatment at 60V15 minutes
  • the dispersion liquid has a pH of 9.5
  • the graph indicated by 4 is an example in which the second anodizing treatment is performed at 40V15 minutes, and the dispersion liquid during electrophoresis has a pH of 9.5.
  • Each graph has a peak around 120 seconds, but the graphs 2 to 4 clearly show that electrophoresis was performed at a higher current density for a longer time than the graph of 1.
  • Example 2 Metal plate anodizing process
  • the pigment sol solution used for electrophoresis is a peptized titanium oxide sol (containing 20% by weight in terms of titanium oxide, primary average particle diameter 6 nm, anatase type, neutral, solvent is water) with the pH of triethanolamine and triethylamine. It is adjusted by adding and applied to a disperser.
  • the titanium oxide concentration in the pigment sol solution is 0.5% by weight, and the electrophoresis conditions are the same as in Example 1.
  • the treatment after the titanium oxide pigment was filled in the pores of the aluminum plate was only water washing.
  • FIG. 3A shows a surface SEM image of the treated aluminum plate
  • FIG. 3A shows a mapping image of titanium atoms by EDX image analysis
  • FIG. 3C shows a mapping image of titanium atoms in a cross section by EDX image analysis
  • FIG. 3 (d) shows the analysis result of the presence of titanium atoms, oxygen atoms, and aluminum atoms in the depth direction of the aluminum plate by rf-GD-OES (high frequency glow discharge luminescence surface analysis).
  • rf-GD-OES high frequency glow discharge luminescence surface analysis
  • the surface of the aluminum plate corresponds to a region where there are some titanium atoms indicated by the bright dots at the top of the figure, and the bright spots indicating the lower titanium atoms in the figure are concentrated.
  • the belt-shaped portion indicates that the titanium oxide pigment is present in the depths of the pores.
  • FIG. 3D shows this tendency as another result. It is a figure in which the processed aluminum plate was sputtered and the types of atoms detected at the same time were confirmed, but the time when the sputtering time was 0 seconds was deeper from the surface as time passed on the surface of the processed aluminum plate. Measures the atoms present at the location.
  • the intensity of titanium atoms has a peak of about 0.3, and after that, when the time exceeds 300 seconds, it shows a peak exceeding 0.5. Will go down.
  • the intensity of oxygen atoms rises and falls within a range of about 1 to 1.5 from the start of sputtering to around 350 seconds, and the intensity decreases after 400 seconds.
  • aluminum has a strength of about 0.5 until 350 seconds, but suddenly becomes stronger after that.
  • the strength of titanium is 500 times greater than the strength of aluminum and oxygen.
  • titanium oxide is also present on the surface portion, but thereafter it can be seen that there is a layer in which the content of titanium oxide increases from 250 seconds to over 350 seconds.
  • the treated aluminum plate has a large number of pores directed in the thickness direction on the surface thereof, and the titanium oxide pigment is deep into the pores. Can be understood.
  • the color of the surface of the aluminum plate exhibits a color that strongly reflects the color of the titanium oxide pigment and has a white color. And since the surface of the obtained aluminum plate was not etched, the obtained coloring was a more vivid color without being matted.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Metallurgy (AREA)
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Abstract

L'invention a pour objet la fourniture d'un article façonné en aluminium dans lequel des pores formés par oxydation anodique sont remplis d'un pigment, l'article façonné en aluminium ayant un film coloré de manière adéquate. Pour ce faire, elle concerne un article façonné en aluminium ayant un film d'oxyde anodique formé sur sa surface, des pores formés dans le film d'oxydation anodique étant remplis d'un pigment de couleur.　
PCT/JP2015/055146 2014-02-28 2015-02-24 Article coloré façonné en aluminium et son procédé de fabrication WO2015129660A1 (fr)

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US15/121,280 US20160362808A1 (en) 2014-02-28 2015-02-24 Colored shaped aluminum article and method for manufacturing same
JP2016505220A JP6720073B2 (ja) 2014-02-28 2015-02-24 着色アルミニウム成形体及びその製造方法
CN201580010252.5A CN106068338A (zh) 2014-02-28 2015-02-24 着色铝成形体及其制造方法

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JP2014038555 2014-02-28
JP2014-038555 2014-02-28

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JPWO2018128123A1 (ja) * 2017-01-04 2019-11-07 株式会社サクラクレパス 色素含有アルマイト処理プラズマインジケータ

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JP6306897B2 (ja) * 2014-02-28 2018-04-04 株式会社サクラクレパス 着色アルミニウム成形体及びその製造方法
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