JPS6259193B2 - - Google Patents
Info
- Publication number
- JPS6259193B2 JPS6259193B2 JP10574783A JP10574783A JPS6259193B2 JP S6259193 B2 JPS6259193 B2 JP S6259193B2 JP 10574783 A JP10574783 A JP 10574783A JP 10574783 A JP10574783 A JP 10574783A JP S6259193 B2 JPS6259193 B2 JP S6259193B2
- Authority
- JP
- Japan
- Prior art keywords
- aluminum alloy
- age hardening
- treatment
- hardening treatment
- pattern
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- 238000011282 treatment Methods 0.000 claims description 122
- 229910000838 Al alloy Inorganic materials 0.000 claims description 106
- 238000003483 aging Methods 0.000 claims description 83
- 238000000034 method Methods 0.000 claims description 67
- 238000005868 electrolysis reaction Methods 0.000 claims description 21
- 238000001125 extrusion Methods 0.000 claims description 15
- 150000007522 mineralic acids Chemical class 0.000 claims description 14
- 239000010407 anodic oxide Substances 0.000 claims description 12
- 150000007524 organic acids Chemical class 0.000 claims description 12
- 238000004381 surface treatment Methods 0.000 claims description 9
- 238000007796 conventional method Methods 0.000 claims description 8
- 238000000059 patterning Methods 0.000 claims description 3
- 238000004040 coloring Methods 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 19
- 230000032683 aging Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 16
- 239000008151 electrolyte solution Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000007743 anodising Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- BZOVBIIWPDQIHF-UHFFFAOYSA-N 3-hydroxy-2-methylbenzenesulfonic acid Chemical compound CC1=C(O)C=CC=C1S(O)(=O)=O BZOVBIIWPDQIHF-UHFFFAOYSA-N 0.000 description 1
- SDGNNLQZAPXALR-UHFFFAOYSA-N 3-sulfophthalic acid Chemical compound OC(=O)C1=CC=CC(S(O)(=O)=O)=C1C(O)=O SDGNNLQZAPXALR-UHFFFAOYSA-N 0.000 description 1
- 229910021365 Al-Mg-Si alloy Inorganic materials 0.000 description 1
- 229910018131 Al-Mn Inorganic materials 0.000 description 1
- 229910018461 Al—Mn Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LSVVNVHHHMEPJZ-UHFFFAOYSA-L [Na+].[Na+].[O-]S(=O)(=O)SS([O-])(=O)=O Chemical compound [Na+].[Na+].[O-]S(=O)(=O)SS([O-])(=O)=O LSVVNVHHHMEPJZ-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- -1 alternating current Substances 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 150000003892 tartrate salts Chemical class 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
【発明の詳細な説明】
発明の技術分野
本発明は、時効硬化性能を有するアルミニウム
合金（純アルミニウムは除く）の表面に、木目
調、プリント調等の各種装飾模様を鮮明に生成で
きる表面処理方法に関するものであり、さらに詳
しくは、アルミニウム合金の表面に二段階時効硬
化処理、機械的操作による下地模様処理、及び電
気化学的処理を巧みに組み合わせて施すことによ
り、極めて施すことにより、極めて簡単な方法
で、アルミニウム合金表面に濃淡差のある美麗な
着色模様を生成できると共に耐食性のある着色皮
膜を形成できるアルミニウム合金の模様付け表面
処理方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention provides a surface treatment method that can clearly produce various decorative patterns such as woodgrain or printed patterns on the surface of an aluminum alloy (excluding pure aluminum) that has age hardening performance. More specifically, by applying a skillful combination of two-step age hardening treatment, a base pattern treatment by mechanical manipulation, and an electrochemical treatment to the surface of an aluminum alloy, it is possible to apply an extremely simple process. The present invention relates to a method for treating the patterned surface of an aluminum alloy, which can produce a beautiful colored pattern with different shading on the surface of the aluminum alloy, and can also form a colored film with corrosion resistance.
従来技術とその問題点
従来、アルミニウム材の表面に、人工時効硬化
処理を利用して着色模様を生成させる方法として
は、特開昭53―83941号が知られている。この技
術は、アルミニウム材の素材表面に所望の模様入
りシートを付着し、これを通常の条件下で人工時
効硬化処理した後、冷却前または後は前記模様入
りシートを取除き、次いでそのアルミニウム材を
陽極として電解着色処理を行なうことによつて、
アルミニウム材の表面に着色模様を生成させる方
法である。そして、この方法における着色模様の
生成機構は、時効硬化処理中にアルミニウム材に
模様入りシートの付着している部分と付着してい
ない部分とに加熱による結晶構造の差異をもたら
すことによつて、その後の電解着色時に模様を生
成させるものである。Prior Art and its Problems Japanese Patent Application Laid-Open No. 83941/1983 is known as a method of producing a colored pattern on the surface of an aluminum material by using artificial age hardening treatment. This technology involves attaching a desired patterned sheet to the surface of an aluminum material, subjecting it to artificial age hardening under normal conditions, removing the patterned sheet before or after cooling, and then removing the patterned sheet from the aluminum material. By performing an electrolytic coloring treatment using the material as an anode,
This method creates a colored pattern on the surface of an aluminum material. The generation mechanism of the colored pattern in this method is that during the age hardening treatment, heating causes a difference in the crystal structure between the portions of the aluminum material to which the patterned sheet is attached and the portions to which the patterned sheet is not attached. A pattern is created during subsequent electrolytic coloring.
しかしながら、この技術は以下の不具合を有す
る。 However, this technique has the following drawbacks.
ａ 時効硬化処理炉内は、左右、上下、前後の各
端部と中央部の温度が必ずしも均一でなく、温
度差があるため、得られる製品の模様のコント
ロールが難かしい。a The temperature inside the age hardening furnace is not necessarily uniform between the left and right, top and bottom, front and rear ends and the center, and there are temperature differences, making it difficult to control the pattern of the resulting product.
ｂ アルミニウム材の熱伝導は非常に良好である
ので、模様入りシートの付着部分と付着してい
ない部分との温度差を出すことに困難性を伴な
う。従つて、鮮明な濃淡差のある着色模様の生
成は困難であり、また、例えば斑点模様、水玉
模様、木目調模様等の小さな模様をアルミニウ
ム材に表出させることは困難である。b. Since aluminum material has very good thermal conductivity, it is difficult to create a temperature difference between the areas where the patterned sheet is attached and the areas where it is not attached. Therefore, it is difficult to produce a colored pattern with a clear difference in shading, and it is also difficult to make small patterns such as a spotted pattern, a polka dot pattern, and a woodgrain pattern appear on an aluminum material.
ｃ 模様入りシートを付着する工程、及び脱着す
る工程が必要であり、また、押出形材の形状毎
に模様入りシートを用意しなければならないの
で、極めて作業性が悪く、得られる製品もコス
ト高になる。c. A process of attaching and detaching the patterned sheet is required, and a patterned sheet must be prepared for each shape of the extruded shape, so the workability is extremely poor and the resulting product is expensive. become.
また、他の模様付き酸化皮膜の形成方法とし
ては、特公昭43―6365号に記載の方法が知られ
ている。この技術は、Al―Mn―Mg系合金の組
成を特別に選定したアルミニウム合金を使用
し、該アルミニウム合金を展伸加工し、該加工
工程中または加工後に特別の熱処理を加え、そ
の後陽極酸化処理することにより、アルミニウ
ム合金表面にAl―Mn二元化合物の析出に起因
するコントラストのある黒白模様を生成させる
方法である。 Furthermore, as another method for forming a patterned oxide film, the method described in Japanese Patent Publication No. 43-6365 is known. This technology uses an aluminum alloy with a specially selected Al-Mn-Mg alloy composition, stretches the aluminum alloy, applies special heat treatment during or after the processing process, and then anodizes the aluminum alloy. This method creates a contrasting black and white pattern on the aluminum alloy surface due to the precipitation of the Al-Mn binary compound.
この方法によつて得られる模様は、その形態が
全くランダムであり、任意の模様が得られないと
共に、その模様も黒白のコントラストに限定され
るため、装飾性のある美麗な着色模様が依然とし
て得られないという不具合を有する。 The patterns obtained by this method are completely random in form, cannot obtain arbitrary patterns, and are limited to the contrast of black and white, so it is still possible to obtain decorative and beautiful colored patterns. The problem is that it cannot be used.
発明の目的
従つて、本発明の第１の目的は、アルミニウム
合金表面に美麗な木目調、プリント調等各種所望
の着色模様を生成できるアルミニウム合金の模様
付け表面処理方法を提供することにある。OBJECTS OF THE INVENTION Accordingly, the first object of the present invention is to provide a patterning surface treatment method for aluminum alloys that can produce various desired colored patterns such as beautiful woodgrain or printed patterns on the surface of aluminum alloys.
本発明の第２の目的は、上記目的と関連して、
耐食性、耐候性、耐摩耗性等各種性能に優れた着
色模様の生成とアルミニウム合金への機械的強
度、特に硬度の付与を、一連の工程で行なえるア
ルミニウム合金の模様付け表面処理方法を提供す
ることにある。 A second object of the present invention, in conjunction with the above object, is to
To provide a patterned surface treatment method for an aluminum alloy that can generate a colored pattern with excellent various properties such as corrosion resistance, weather resistance, and abrasion resistance, and impart mechanical strength, especially hardness, to the aluminum alloy in a series of steps. There is a particular thing.
本発明のさらに第３の目的は、前記目的と関連
して、着色模様をさらに濃淡差のある極めて鮮明
な着色模様とすることのできるアルミニウム合金
の模様付け表面処理方法を提供することにある。 A third object of the present invention, in conjunction with the above-mentioned object, is to provide a patterned surface treatment method for an aluminum alloy, which allows the colored pattern to be an extremely clear colored pattern with further shading differences.
本発明のさらに他の目的は、前記目的と関連し
て、着色模様のコントラストがより鮮明であると
共に着色性に極めて優れたアルミニウム合金の模
様付け表面処理方法を提供することにある。 Still another object of the present invention, in conjunction with the above object, is to provide a patterned surface treatment method for an aluminum alloy, which provides a clearer contrast in the colored pattern and has extremely excellent colorability.
発明の構成
本発明は、押出成型後のアルミニウム合金に、
従来から一般に行なわれている押出成型後の完全
時効硬化処理に代えて、１次不完全時効硬化処理
後、機械的操作により下地模様を施し、その後前
記１次不完全時効硬化処理より高い温度条件で２
次不完全乃至完全時効硬化処理を行ない、さらに
該アルミニウム合金に電気化学的操作により着色
皮膜を施すことにより、前記二段階の不完全乃至
完全時効硬化処理によつてより高い硬度を一連の
工程でアルミニウム合金に付与できると共に、前
記各工程の相剰作用により、着色皮膜形成工程に
おいて、前記下地模様部分と背景（模様部分以外
の部分）との間に着色の濃淡差が生じ、アルミニ
ウム合金の表面に前記下地模様が極めて鮮明に表
出するという知見に基づくものであり、さらに、
前記着色皮膜形成工程に酸化皮膜改質工程を付加
することにより、前記基本的方法で得られる着色
模様を、さらに濃淡差のある極めて鮮明な着色模
様に改良できるという知見にも基づくものであ
る。Structure of the Invention The present invention provides an aluminum alloy after extrusion molding.
Instead of the conventional complete age hardening treatment after extrusion molding, which has been commonly done in the past, a base pattern is applied by mechanical operation after the first incomplete age hardening treatment, and then a temperature condition higher than that of the first incomplete age hardening treatment is applied. So 2
Next, by performing incomplete to complete age hardening treatment, and further applying a colored film to the aluminum alloy by electrochemical operation, higher hardness can be achieved in a series of steps through the above two stages of incomplete to complete age hardening treatment. Not only can it be applied to the aluminum alloy, but also due to the mutual effect of the above-mentioned steps, a difference in the shade of color occurs between the base pattern part and the background (parts other than the pattern part) in the colored film forming process, and the surface of the aluminum alloy is This is based on the knowledge that the base pattern appears extremely clearly, and further,
It is also based on the knowledge that by adding an oxide film modification step to the colored film forming step, the colored pattern obtained by the basic method can be further improved to an extremely clear colored pattern with a difference in shading.
すなわち、本発明に係る第１の発明は、前記第
１及び第２の発明の目的に対応するものであつ
て、
(A) 押出成型後のアルミニウム合金に１次不完全
時効硬化処理を施し、
(B) 次いで、該アルミニウム合金表面に機械的操
作による下地模様を施した後、
(C) 前記１次不完全時効硬化処理の処理温度より
高い温度条件で２次不完全時効硬化処理乃至完
全時効硬化処理を施し、
(D) しかる後、前記アルミニウム合金表面に着色
皮膜を形成する。 That is, the first invention according to the present invention corresponds to the objects of the first and second inventions, and includes: (A) performing a primary incomplete age hardening treatment on an aluminum alloy after extrusion molding; (B) Next, after applying a base pattern to the aluminum alloy surface by mechanical manipulation, (C) performing a second incomplete age hardening treatment or complete aging at a temperature higher than the treatment temperature of the first incomplete age hardening treatment. A hardening treatment is performed, and (D) a colored film is then formed on the surface of the aluminum alloy.
という基本構成を採るものである。The basic structure is as follows.
また、本発明に係る第２の発明は、前記第１乃
至第４の発明の目的に対応するものであつて、上
記第１の発明の(D)工程に代えて、前記(A)〜(C)の各
工程後、
(D′) (i) 前記アルミニウム合金に常法による陽
極酸化皮膜を形成し、
(ii) 続いて無機酸及び／又は有機酸浴中で交流
電解して前記陽極酸化皮膜を二重皮膜構造に
改質した後、
(iii) 該皮膜に着色処理を施す
という構成を採用するものである。 Moreover, the second invention according to the present invention corresponds to the object of the first to fourth inventions, and replaces the step (D) of the first invention with the steps (A) to ( After each step of C), (D') (i) forming an anodic oxide film on the aluminum alloy by a conventional method; (ii) then performing alternating current electrolysis in an inorganic acid and/or organic acid bath to remove the anodic oxidation film; After modifying the film into a double film structure, (iii) the film is subjected to a coloring treatment.
さらに、本発明に係る第３の発明は、前記第１
乃至第４の発明の目的に対応するものであつて、
上記第１の発明の(D)工程に代えて、前記(A)〜(C)の
各工程後、
(D″) (i) 前記アルミニウム合金に常法による陽
極酸化皮膜を形成し、
(ii) 続いて無機酸及び／又は有機酸浴中で前記
アルミニウム合金を陰極に接続して直流電解
することによつて前記陽極酸化皮膜を改質し
た後、
(iii) 該皮膜に着色処理を施す
という構成を採用するものである。 Furthermore, the third invention according to the present invention provides the first aspect of the present invention.
Corresponding to the purpose of the fourth invention,
Instead of step (D) of the first invention, after each step of (A) to (C), (D″) (i) forming an anodized film on the aluminum alloy by a conventional method; (ii) ) Subsequently, the aluminum alloy is connected to a cathode in an inorganic acid and/or organic acid bath and the anodic oxide film is modified by direct current electrolysis, and (iii) the film is subjected to a coloring treatment. The configuration is adopted.
発明の態様
次に、前記本発明の各工程及びその態様につい
て詳細に説明する。Aspects of the Invention Next, each step of the present invention and its aspects will be explained in detail.
(A) １次不完全時効硬化処理工程
まず、押出成型後のアルミニウム合金（以下、
アルミニウム合金と略称する）の押出形材に、１
次不完全時効硬化処理を施す。(A) First incomplete age hardening treatment process First, the aluminum alloy after extrusion molding (hereinafter referred to as
1 to the extruded shape of aluminum alloy)
Next, perform incomplete age hardening treatment.
１次時効硬化処理は、アルミニウム合金が完全
時効に至らない条件で行なう。 The primary age hardening treatment is performed under conditions where the aluminum alloy does not reach complete aging.
時効硬化処理について説明すると、例えばアル
ミ合金Ａ―6063S材の場合、時効硬化温度と時間
との合金の硬度に及ぼす影響は第１図に示すとお
りである。すなわち、いずれの温度においてもあ
る時間経過後に硬度は最大値となり、この段階の
時効硬化を完全時効硬化と定義する。従つて、不
完全時効硬化とは、この段階に達する以前の時効
硬化を意味する。 To explain age hardening treatment, for example, in the case of aluminum alloy A-6063S material, the influence of age hardening temperature and time on the hardness of the alloy is as shown in FIG. That is, the hardness reaches its maximum value after a certain period of time at any temperature, and age hardening at this stage is defined as complete age hardening. Therefore, incomplete age hardening means age hardening before reaching this stage.
第１図は高温時効あるいは人工時効の状態を示
すが、ここでいう不完全時効はこれのみに限られ
ず、室温時効あるいは自然時効をも含むものであ
る。従つて、極端なことをいえば、長時間放置し
て自然時効してもよい。しかし、通常は作業性や
後述する２次時効硬化処理との関係からも人工時
効硬化処理を施すことが好ましく、この場合、ア
ルミ合金の材質によつても相違するが、一般に
145〜185℃の温度条件で0.5〜10時間行なうこと
が好ましい（第３図参照）。また、後述する２次
時効硬化処理とも関連して適正条件を設定すれば
よい。 Although FIG. 1 shows the state of high-temperature aging or artificial aging, incomplete aging here is not limited to this, but also includes room temperature aging or natural aging. Therefore, in an extreme case, it may be allowed to stand for a long time to age naturally. However, it is usually preferable to perform artificial age hardening treatment from the viewpoint of workability and the relationship with the secondary age hardening treatment described below.In this case, although it varies depending on the material of the aluminum alloy, generally
It is preferable to carry out the reaction at a temperature of 145 to 185°C for 0.5 to 10 hours (see Figure 3). Further, appropriate conditions may be set in conjunction with the secondary age hardening treatment described later.
(B) 下地模様形成工程
前記のように、１次不完全時効硬化処理された
アルミ合金の押出形材（１次時効硬化処理直後の
高温状態の押出形材でもよいし、冷却後の常温の
押出形材でもよい）に、次に機械的操作により下
地模様を施す。(B) Base pattern forming process As mentioned above, the extruded shape of aluminum alloy that has been subjected to the first incomplete age hardening treatment (the extruded shape at a high temperature immediately after the first age hardening treatment may be used, or the extruded shape at room temperature after cooling) (which may be extruded profiles) is then provided with a base pattern by mechanical manipulation.
機械的操作とは、酸、アルカリによる蝕刻など
化学的処理以外の全ての操作を含む。 Mechanical operations include all operations other than chemical treatments such as etching with acids and alkalis.
この下地模様は、例えば、砂、鉄粉等を吹き付
けるプラスト法、水等の液体を高圧で噴射する高
圧噴射法、ブラシによりアルミ合金表面を傷付け
るブラシ法、レーザー光線を照射するレーザー光
線法、エンボス版ロールを使用するローラー法、
型プレスにより圧刻するプレス法等の各種機械的
操作手段によりアルミ合金表面に施される。 This base pattern can be created using, for example, the plasto method in which sand, iron powder, etc. are sprayed, the high-pressure injection method in which water or other liquid is injected at high pressure, the brush method in which the aluminum alloy surface is scratched with a brush, the laser beam method in which the surface is irradiated with a laser beam, or the embossed plate roll. roller method using
It is applied to the surface of an aluminum alloy by various mechanical operation means such as a press method in which stamping is performed using a mold press.
より具体的に説明すれば、例えば作業性の向上
を狙い、アルミ合金の押出金型と同形状で一定間
隔のクリアランスのある金型もしくは金枠（治
具）に、例えば柾目模様間隔に高圧噴射の噴射溝
（穴）を設け、水または研摩剤等を噴射しながら
連続的に表面調整（下地模様付与）することによ
り、複雑な形状の凹凸部にも下地模様を施すこと
ができる。この場合、所望の連続模様（例えば、
印刷の如く長く通つた柾目の間隔、ぼかしに変化
のある模様等）を容易に付与できる。また、上記
高圧噴射に代えて、金型もしくは金枠内部に、例
えば柾目模様間隔に金属またはセラミツクの爪状
の治具を配設し、これによつて一定圧力でアルミ
合金形材をこする方法も採用できる。 To be more specific, for example, with the aim of improving workability, high-pressure injection is applied to a mold or metal frame (jig) that has the same shape as an aluminum alloy extrusion mold and has a certain amount of clearance, for example, at straight-grain intervals. By providing spray grooves (holes) and continuously adjusting the surface (applying a base pattern) while spraying water or an abrasive, it is possible to apply a base pattern to even complex-shaped irregularities. In this case, the desired continuous pattern (e.g.
It is possible to easily create patterns (like printing, with long straight-grain intervals, patterns with varying shading, etc.). In addition, instead of the above-mentioned high-pressure injection, metal or ceramic claw-shaped jigs are arranged inside the mold or metal frame, for example, at intervals of a straight grain pattern, and are used to rub the aluminum alloy shape with a constant pressure. method can also be adopted.
また、１次不完全時効硬化処理されたアルミ合
金形材を、キズもしくはヒズミを与える装置、例
えばエンボス版ロールにて任意の模様に圧刻する
ことにより、柾目、板目、文字、絵等の所望の模
様が容易に形成でき、装飾性をより高めることが
できる。さらに、パネル関係においては、型プレ
スによる圧刻もでき、複雑な任意の模様を付与で
きる。 In addition, by stamping the aluminum alloy shape that has been subjected to the primary incomplete age hardening treatment into an arbitrary pattern using a device that creates scratches or distortions, such as an embossing roll, straight grain, board grain, letters, pictures, etc. can be created. Desired patterns can be easily formed and decorativeness can be further enhanced. Furthermore, in relation to panels, stamping using a mold press is also possible, and any complex pattern can be imparted.
その他、形材形状との相剰効果法として、押出
成型の段階で形材自体に模様状に凹凸を付け、金
属、セラミツク、カーボン等で表面をこすること
によつても、模様を付与できる。 In addition, as a mutual effect method with the shape of the shape, a pattern can also be imparted by creating irregularities in the shape of a pattern on the shape itself during the extrusion molding stage, and by rubbing the surface with metal, ceramic, carbon, etc. .
下地模様の形成手段は、以上の方法のみに限定
されるものではなく、アルミ合金の形材表面に作
業性の良い方法で装飾性のある模様状の表面調整
ができる方法であればよい。 The means for forming the base pattern is not limited to the above methods, but any method may be used as long as it can form a decorative pattern on the surface of the aluminum alloy profile using a method with good workability.
この下地模様の形成は、その後の時効硬化処理
（２次不完全乃至完全時効硬化処理）と電気化学
的着色処理との相剰作用により、着色模様表出の
下地乃至核となるものであり、キズ部の凹部深さ
は表面調整（下地模様形成）の下可欠要素ではな
く、外観上合格となる程度のダイスマーク以内で
充分であり、その後の酸化皮膜生成後の状態にお
いても、顕微鏡による観察でもそのキズによる性
能低下は全く認められない程度のものである。ま
た、ヒズミを与えた部分も同様であり、性能の低
下は全くない。 The formation of this base pattern becomes the base or nucleus for the appearance of the colored pattern due to the interaction of the subsequent age hardening treatment (secondary incomplete to complete age hardening treatment) and electrochemical coloring treatment, The depth of the concave part of the scratched part is not an essential element for surface preparation (base pattern formation), but it is sufficient to be within the dice mark that passes the appearance, and even after the oxide film is formed, it is Even by observation, there was no noticeable deterioration in performance due to the scratches. Further, the same applies to the parts where distortion is applied, and there is no deterioration in performance at all.
(C) ２次不完全乃至完全時効硬化処理工程
これは、不完全時効硬化でもよいし、完全時効
硬化でもよいという意味である。この２次時効硬
化処理は、前記１次時効硬化処理の処理温度より
も高い温度条件で行なう。(C) Secondary incomplete to complete age hardening treatment step This means that either incomplete age hardening or complete age hardening may be used. This secondary age hardening treatment is performed at a temperature higher than the treatment temperature of the primary age hardening treatment.
前記１次及び２次の２段階時効硬化処理による
効果について、例えばＡ―6063S合金における１
次時効（160℃）及び２次時効（190℃）の組合せ
及びその条件による効果を第２図に示す。 Regarding the effect of the two-stage age hardening treatment, for example, 1 in A-6063S alloy.
Figure 2 shows the combination of secondary aging (160°C) and secondary aging (190°C) and the effects of the conditions.
第２図は、１次時効―冷却―２次時効の処理の
効果を示すものであるが、前記のように１次時効
と２次時効の間に下地模様形成工程を入れた場合
でも、上記２段階時効硬化処理に相違なく、第２
図に示すのと同等の効果が得られる。 Figure 2 shows the effect of the primary aging - cooling - secondary aging process. There is no difference in the two-stage age hardening treatment, and the second
The same effect as shown in the figure can be obtained.
第２図から明らかなように、いずれの条件にお
いても、１次時効と２次時効の組合せは、190℃
×6hrの１段完全時効硬化処理よりも硬度が高く
なるという効果がある。この効果が得られる１次
と２次の時効硬化処理の組合せにより、その後の
着色処理(D)，（D′），（D″）によりキズまたはヒズ
ミ等の表面調整した箇所（下地模様部分）が濃色
となり、着色コントラストのある模様を現出させ
ることができる。他の効果としては、陽極酸化処
理、電解発色処理、酸化皮膜改質処理、電解着色
処理等の電解処理前に、アルミ合金に充分な硬度
を入れることができる、ということが挙げられ
る。 As is clear from Figure 2, under all conditions, the combination of primary aging and secondary aging is 190°C.
The effect is that the hardness is higher than the one-stage complete age hardening treatment of ×6 hours. By combining the primary and secondary age hardening treatments that achieve this effect, the subsequent coloring treatments (D), (D'), and (D'') are applied to areas where the surface has been adjusted to remove scratches or distortions (base pattern areas). The color of the aluminum alloy becomes dark and a pattern with contrasting color appears.Another effect is that the aluminum alloy is treated with aluminum alloy before electrolytic treatment such as anodizing treatment, electrolytic coloring treatment, oxide film modification treatment, and electrolytic coloring treatment. One example is that sufficient hardness can be added to the material.
なお、第２図は１次と２次の時効硬化処理の間
に常温まで冷却した場合の結果であるが、１次時
効と２次時効との間に冷却工程を入れないと前記
した効果が少なくなる。従つて、１次と２次の時
効硬化処理の間（下地模様形成工程の前または
後）には冷却工程を入れることが好ましく、これ
によつて単なる２段階時効硬化処理よりも、硬度
がさらに大きく、かつその後の着色処理により前
記下地模様部分と背景（非模様付与部）との着色
濃淡差がさらに大きくなる。 Note that Figure 2 shows the results when cooling to room temperature between the primary and secondary age hardening treatments, but the effect described above will not occur unless a cooling process is included between the primary and secondary aging treatments. It becomes less. Therefore, it is preferable to include a cooling process between the primary and secondary age hardening treatments (before or after the base pattern forming process), which will further increase the hardness compared to a simple two-step age hardening process. The difference in color shading between the base pattern portion and the background (non-patterned portion) becomes larger due to the subsequent coloring treatment.
なお、前記(B)１次不完全時効硬化処理の温度と
(C)２次不完全時効硬化処理乃至２次完全時効硬化
処理の温度との温度差は５℃〜60℃に設定するの
が好ましい。その理由は、５℃未満の場合には、
時効硬化処理を２段階に分けたことによる効果が
明瞭に現われず、充分な硬度及び着色処理におけ
る充分な着色濃淡差が得られないためである。ま
た、上限を60℃と設定した理由は、これ以上の温
度差がある場合は、１次不完全時効硬化処理温度
が低くなるため、処理時間が長くなり、製造工程
における効率が悪くなり、不経済であるからであ
る。 In addition, the temperature of the (B) primary incomplete age hardening treatment and
(C) The temperature difference from the temperature of the secondary incomplete age hardening treatment to the secondary complete age hardening treatment is preferably set to 5°C to 60°C. The reason is that if the temperature is less than 5℃,
This is because the effect of dividing the age hardening treatment into two stages is not clearly seen, and sufficient hardness and sufficient difference in color shading during the coloring treatment cannot be obtained. The reason why the upper limit was set at 60℃ is that if there is a temperature difference greater than this, the temperature for the primary incomplete age hardening treatment will be lower, which will lengthen the treatment time, reduce efficiency in the manufacturing process, and cause problems. This is because it is an economic matter.
また、２段階時効硬化処理における１次不完全
時効硬化処理の時間と温度の適正範囲を第３図に
示す。斜線内の領域は特に好ましい範囲である。
なお、２次の時効硬化処理の時間は少なくとも１
時間以上を必要とする。 Moreover, the appropriate range of time and temperature for the first incomplete age hardening treatment in the two-stage age hardening treatment is shown in FIG. The area within the hatched area is a particularly preferred range.
In addition, the time of the secondary age hardening treatment is at least 1
Requires more than time.
(D) 着色皮膜処理工程
前記各工程(A)〜(C)を経たアルミ合金を、通常の
方法により脱脂、水洗、必要に応じてスマツト除
去等の処置を施した後、周知である次のいずれか
の方法により前記アルミ合金表面に着色酸化皮膜
を形成する。(D) Colored film treatment process The aluminum alloy that has gone through each of the above steps (A) to (C) is subjected to treatments such as degreasing, washing with water, and removal of smut as necessary by the usual method, and then undergoing the following well-known process. A colored oxide film is formed on the surface of the aluminum alloy by any method.
ａ 無機酸及び／又は有機酸の電解液中で、直流
または交流もしくはこれらに類似の電流波形を
使用して、前記アルミ合金を陽極酸化処理した
後、無機金属塩を含む電解液中で交流電解また
は直流陰極電解して着色皮膜を形成する。a. After anodizing the aluminum alloy in an electrolytic solution containing an inorganic acid and/or an organic acid using direct current, alternating current, or a current waveform similar to these, alternating current electrolysis is performed in an electrolytic solution containing an inorganic metal salt. Alternatively, a colored film is formed by direct current cathode electrolysis.
いわゆる陽極酸化―電解着色によつて着色皮
膜を形成するものである。陽極酸化に使用する
電解質としては周知の無機酸及び／又は有機
酸、例えば硫酸、クロム酸、リン酸等、あるい
はこれらの混酸液、シユウ酸、マロン酸等ある
いはこれらのまたは無機酸との混酸液など、周
知の電解質が使用でき、陽極酸化の印加電圧及
び印加時間等も常法通りで充分である。 A colored film is formed by so-called anodic oxidation-electrolytic coloring. As the electrolyte used for anodizing, well-known inorganic acids and/or organic acids such as sulfuric acid, chromic acid, phosphoric acid, etc., mixed acid solutions thereof, oxalic acid, malonic acid, etc., or mixed acid solutions of these or with inorganic acids are used. Well-known electrolytes such as the following can be used, and the applied voltage and application time for anodic oxidation are sufficient as usual.
電解着色に用いる無機金属塩としても、例え
ばニツケル、コバルト、クロム、銅、カドミウ
ム、チタン、マンガン、モリブデン、スズ、マ
グネシウム、銀、鉛等の硫酸塩、塩酸塩、シユ
ウ酸塩、酒石酸塩、クロム酸塩、リン酸塩等、
従来周知の各種塩が使用でき、また電解条件も
常法通りで充分である。 Examples of inorganic metal salts used for electrolytic coloring include sulfates, hydrochlorides, oxalates, tartrates, and chromium such as nickel, cobalt, chromium, copper, cadmium, titanium, manganese, molybdenum, tin, magnesium, silver, and lead. acid salts, phosphates, etc.
Various conventionally known salts can be used, and conventional electrolytic conditions are sufficient.
ｂ 無機酸に金属塩を添加した電解液、または有
機酸を含む電解液中で、アルミ合金表面に陽極
酸化皮膜を形成すると同時に着色する電解発色
法により着色皮膜を形成する。b. A colored film is formed by an electrolytic coloring method in which an anodized film is formed on the aluminum alloy surface and colored at the same time in an electrolytic solution containing an inorganic acid and a metal salt, or an electrolytic solution containing an organic acid.
エマタル法、カルカラー（Kalcolor）法等各
種方法が知られており、また陽極酸化皮膜が発
色を起す有機酸としてはシユウ酸、マロン酸、
スルホサリチル酸、スルホフタル酸、マレイン
酸、酒石酸等各種の酸あるいは混酸液が知られ
ている。 Various methods are known, such as the ematal method and the Kalcolor method, and the organic acids that cause the anodic oxide film to develop color include oxalic acid, malonic acid,
Various acids or mixed acid solutions are known, such as sulfosalicylic acid, sulfophthalic acid, maleic acid, and tartaric acid.
ｃ 無機酸を含む電解液中で、自然発色合金から
成るアルミ合金表面に陽極酸化皮膜を形成する
と同時に発色させる自然発色法により、着色皮
膜を形成する。c. A colored film is formed by a natural coloring method in which an anodized film is formed on the surface of an aluminum alloy made of a naturally colored alloy in an electrolytic solution containing an inorganic acid, and at the same time the color develops.
別名、合金発色法としても知られ、アルミニ
ウム中に添加された金属の影響により陽極酸化
すると発色するものであり、その合金成分特有
の着色を呈する。一般に、含有成分がCrの場
合鮮黄色系、Cuの場合黄褐色系、Siの場合黒
色系、Mnの場合ピンク系となることが知られ
ており、またAl―Mn―Cr系合金ではMn及び
Crが固溶状態の場合はブロンズ色、析出状態
では黒色となるほど、熱処理の条件等によつて
も異なつた着色を示す。 Also known as the alloy coloring method, this method develops color when anodic oxidation is performed due to the influence of metals added to aluminum, and the coloration is unique to the alloy components. In general, it is known that when the content is Cr, the color is bright yellow, when it is Cu, it is yellowish brown, when it is Si, it is black, and when it is Mn, it is pink.
The coloring varies depending on the heat treatment conditions, such as bronze color when Cr is in a solid solution state and black color when it is in a precipitated state.
以上のような各種方法により電気化学的に着色
処理することにより、耐食性や耐候性に優れた着
色皮膜が形成されると共に、前記下地模様部分
（キズもしくはヒズミ部）が背景（非模様付与
部）よりも濃く着色され、機械的操作によりアル
ミ合金表面に施された下地模様が着色模様として
表出する。 By electrochemically coloring using the various methods described above, a colored film with excellent corrosion resistance and weather resistance is formed, and the base pattern portion (scratches or distortions) is transformed into a background (non-patterned portion). The color is darker than that of the aluminum alloy, and the underlying pattern applied to the aluminum alloy surface by mechanical operation appears as a colored pattern.
このように着色皮膜処理を施されたアルミ合金
は、必要に応じて塗装工程へ送られ、周知の方法
により塗装処理、焼付処理される。 The aluminum alloy that has been subjected to the colored film treatment in this manner is sent to a painting process as required, and is painted and baked by well-known methods.
本発明に係る第２及び第３の発明は、前記第１
の発明の(D)着色皮膜処理工程の代りに、陽極酸化
皮膜処理→酸化皮膜改質処理→着色処理の工程を
採用するものであり、酸化皮膜改質処理の相違に
より以下の２つの方法に分けられる。 The second and third inventions according to the present invention are the first and third inventions.
In place of the colored film treatment step (D) of the invention, the following two methods are adopted depending on the difference in the oxide film modification treatment. Can be divided.
すなわち、前記(A)〜(C)の各工程後、
(D′) (i) 前記アルミ合金に常法による陽極酸化
皮膜を形成し、
(ii) 続いて無機酸及び／又は有機酸浴中で交流
電解して前記陽極酸化皮膜を二重皮膜構造に
改質した後、
(iii) 該皮膜に着色処理を施す
方法（第２の発明）と、
(D″) (i) 前記アルミニウム合金に常法による陽
極酸化皮膜を形成し、
(ii) 続いて無機酸及び／又は有機酸浴中で前記
アルミニウム合金を陰極に接続して直流電解
することによつて前記陽極酸化皮膜を改質し
た後、
(iii) 該皮膜に着色処理を施す
方法（第３の発明）である。 That is, after each of the steps (A) to (C) above, (D') (i) forming an anodic oxide film on the aluminum alloy by a conventional method, (ii) subsequently bathing in an inorganic acid and/or organic acid bath; after modifying the anodic oxide film into a double film structure by alternating current electrolysis, (iii) a method of coloring the film (second invention); After forming an anodic oxide film by a conventional method, (ii) subsequently modifying the anodic oxide film by connecting the aluminum alloy to a cathode and subjecting it to direct current electrolysis in an inorganic acid and/or organic acid bath; (iii) A method of subjecting the film to a coloring treatment (third invention).
前記（D′）(ii)及び（D″）(ii)の酸化皮膜改質処
理は、第１の発明の如く必ずしも不可欠というも
のではないが、模様のコントラストをより鮮明に
する目的で行なう工程である。すなわち、前記着
色皮膜処理(D)自体でも充分な場合もあるが、より
作業性のある条件での処理及び装飾性の向上を狙
い、酸化皮膜改質処理を行なう。 Although the oxide film modification treatments (D′)(ii) and (D″)(ii) are not necessarily essential as in the first invention, they are steps performed for the purpose of making the contrast of the pattern clearer. That is, although the colored film treatment (D) itself may be sufficient in some cases, an oxide film modification treatment is performed with the aim of processing under conditions that are more workable and improving decorative properties.
この条件としては、前記着色皮膜処理(D)の電解
液と同じ電解質あるいはそれに金属塩等添加剤を
加えたもの、または異なる電解質でもよいが、こ
の電解液中で陰極電解するか、交流またはそれと
同等の効果のある波形で電解処理する。例えば、
硫酸浴中での陽極酸化処理後、これと同じ電解液
を用い、カーボンを対極として交流電解を行なう
方法が標準的な組合せである。なお、前記着色皮
膜処理(D)と同じ電解質の電解液で濃度、温度等を
変え、また添加剤の添加等を行なつて、陽極酸化
及び酸化皮膜改質を行なつても同様の効果が得ら
れる。 This condition may be the same electrolyte as the electrolyte used in colored film treatment (D) above, or an electrolyte with additives such as metal salts added thereto, or a different electrolyte, but cathodic electrolysis in this electrolyte, alternating current, or Electrolyte treatment with a waveform that has the same effect. for example,
A standard combination is to perform alternating current electrolysis using the same electrolytic solution and carbon as a counter electrode after anodizing in a sulfuric acid bath. Furthermore, the same effect can be obtained by performing anodic oxidation and modifying the oxide film by changing the concentration, temperature, etc., and adding additives using the same electrolytic solution as in the colored film treatment (D). can get.
以下に各工程毎に説明する。 Each step will be explained below.
(D′)(i)，(D″)(i) 酸化皮膜形成工程
前記(D)(a)で説明したように、無機酸及び／又は
有機酸の電解液中で、直流または交流もしくはこ
れらに類似の電流波形を使用して、アルミ合金を
陽極酸化処理し、酸化皮膜を形成する。印加電
圧、浴温等の電解条件は常法の通りで充分であ
る。(D′)(i), (D″)(i) Oxide film formation process As explained in (D)(a) above, in an electrolyte of inorganic acid and/or organic acid, direct current or alternating current or Using a current waveform similar to the above, the aluminum alloy is anodized to form an oxide film.The electrolytic conditions such as applied voltage and bath temperature are sufficient as usual.
(D′)(ii)，(D″)(ii) 酸化皮膜改質工程
前記のようにして得られたアルミ合金表面の酸
化皮膜を、以下のいずれかの方法で改質する。(D′)(ii), (D″)(ii) Oxide film modification step The oxide film on the surface of the aluminum alloy obtained as described above is modified by one of the following methods.
(D′)(ii) 交流電解改質法
硫酸、リン酸、クロム酸等の無機酸またはシユ
ウ酸等の有機酸からなる電解液中で、アルミ合金
に交流またはこれと同等の性質を有する電流波形
を通電することにより、前記酸化皮膜を二重皮膜
構造に改質する。電解条件は常法の通りで充分で
あるが、好ましくは５〜30V、１〜30分の条件で
行なう。(D′)(ii) AC electrolytic reforming method: Electrolytic reforming method in which alternating current or an electric current having properties equivalent to this is applied to an aluminum alloy in an electrolytic solution consisting of an inorganic acid such as sulfuric acid, phosphoric acid, or chromic acid or an organic acid such as oxalic acid. By applying a waveform current, the oxide film is modified into a double film structure. The electrolytic conditions may be the same as conventional methods, but preferably the electrolysis is carried out at 5 to 30 V for 1 to 30 minutes.
この交流電解による２次陽極酸化処理は、着色
皮膜の生成を目的とするものではなく、前記酸化
皮膜処理と相俟つて二重皮膜構造の酸化皮膜を生
成させるものである。 This secondary anodic oxidation treatment by AC electrolysis is not intended to produce a colored film, but to produce an oxide film with a double film structure in conjunction with the oxide film treatment described above.
この二重皮膜構造の生成によつて、その後の着
色処理により形成された着色模様は、下地模様部
分と背景との着色濃淡差が顕著になり、着色模様
のコントラストがより鮮明になる。 Due to the formation of this double film structure, in the colored pattern formed by the subsequent coloring process, the difference in color shading between the base pattern portion and the background becomes noticeable, and the contrast of the colored pattern becomes clearer.
(D″)(ii) 陰極直流電解改質法
硫酸、リン酸等の無機酸からなる電解液中で、
前記酸化皮膜が形成されたアルミ合金を陰極に接
続して、直流またはこれと同等の性質を有する電
流波形を使用して、前記アルミ合金を通電処理す
る。(D″)(ii) Cathode direct current electrolytic reforming method In an electrolytic solution consisting of an inorganic acid such as sulfuric acid or phosphoric acid,
The aluminum alloy on which the oxide film is formed is connected to a cathode, and the aluminum alloy is energized using a direct current or a current waveform having properties equivalent to the direct current.
この通電処理により、アルミ合金表面の酸化皮
膜に溶解作用が生じるが、この際、下地模様部分
と他の部分（背景）とで電流の流れる量が違うた
め、両者間の皮膜の質に違いが出る。その結果、
その後の着色処理によつて着色模様のコントラス
トがより顕著となる。 This current treatment causes a dissolution effect on the oxide film on the aluminum alloy surface, but at this time, because the amount of current flowing is different between the base pattern and other parts (background), there is a difference in the quality of the film between the two. Get out. the result,
The contrast of the colored pattern becomes more remarkable through the subsequent coloring process.
電解液の濃度、印加電圧、時間等は常法の通り
で充分であるが、好ましくは３〜20V、20秒〜10
分の条件で行なう。 The concentration of the electrolyte, the applied voltage, the time, etc. are sufficient as usual, but preferably 3 to 20 V, 20 seconds to 10
It will be carried out under the following conditions.
(D′)(iii)，(D″)(iii) 着色処理工程
前記工程で改質された酸化皮膜を、前記(D)(a)で
述べた方法で着色する。すなわち、無機金属塩を
含む電解液中で交流電解または直流陰極電解し、
着色皮膜を形成する。(D′)(iii), (D″)(iii) Coloring treatment step The oxide film modified in the above step is colored by the method described in (D)(a) above. AC electrolysis or DC cathodic electrolysis in an electrolyte containing
Forms a colored film.
これによつて、アルミ合金表面に濃淡差のある
極めて鮮明な着色模様が形成される。 As a result, an extremely clear colored pattern with different shading is formed on the aluminum alloy surface.
素材：
本発明では純アルミニウムは除かれるが、各種
アルミニウム合金が使用できる。アルミニウム合
金は、焼入れや焼もどしにより強度を高める合
金、すなわち主要添加物としてCu，Mg＋Si，Zn
＋Mg等を添加したものが好適例として挙げられ
るが、これだけに限定されるものではなく、また
添加元素、加工硬化、熱処理条件等の組合せによ
つて、着色模様の色調、模様のコントラストを調
整できる。また、熱処理効果を高め処理時間の短
縮を図るために、添加元素量を変えることもでき
る。例えば、Al―Mg―Siの合金において、ある
いはMg―Si―Fe合金において、添加量の組合せ
によつて、例えば過剰Siとすることにより、時効
硬化を促進することができる。従つて、色調、模
様のコントラスト、処理工程の作業性改善等を目
的として、その処理工程、条件に合つた合金成分
のアルミニウム合金を用いることができる。Material: Although pure aluminum is excluded in the present invention, various aluminum alloys can be used. Aluminum alloys are alloys whose strength is increased through quenching and tempering, that is, Cu, Mg + Si, and Zn as the main additives.
A suitable example is one with +Mg added, but it is not limited to this, and the tone of the colored pattern and the contrast of the pattern can be adjusted by combining the added elements, work hardening, heat treatment conditions, etc. . Further, in order to enhance the heat treatment effect and shorten the treatment time, the amount of added elements can be changed. For example, in an Al--Mg--Si alloy or in a Mg--Si--Fe alloy, age hardening can be promoted by changing the addition amount, for example, by adding excess Si. Therefore, for the purpose of improving color tone, pattern contrast, workability of processing steps, etc., it is possible to use an aluminum alloy with an alloy component suitable for the processing steps and conditions.
発明の効果
以上のように、本発明に係るアルミニウム合金
の模様付け表面処理方法によれば、機械的操作に
よる下地模様の形成、二段階時効硬化処理、及び
電気化学的着色皮膜の形成の各工程の相剰作用に
より、前記下地模様部分と背景との間に着色濃淡
差が生じ、アルミニウム合金表面に、耐食性、耐
候性、耐摩耗性等各種性能に優れると共に、木目
調、プリント調等各種所望の美麗な着色模様を生
成できる。また、前記酸化皮膜改質工程が付加さ
れることにより、着色濃淡差がさらに大きくな
り、着色模様のコントラストがより鮮明であると
共に着色性に極めて優れた着色模様が得られる。Effects of the Invention As described above, according to the method for patterned surface treatment of aluminum alloy according to the present invention, each step of forming a base pattern by mechanical operation, two-step age hardening treatment, and forming an electrochemical colored film Due to the interaction of It is possible to generate beautiful colored patterns. Furthermore, by adding the oxide film modification step, the difference in color shading becomes even larger, and a colored pattern with clearer contrast and extremely excellent coloring properties can be obtained.
さらに、２段階の時効硬化処理を採用するた
め、アルミニウム合金への機械的強度、特に硬度
の付与を、陽極酸化もしくは着色皮膜形成前に、
一連の工程で完全に行なうことができる。しか
も、２段階の時効硬化処理間に下地模様形成工程
を導入したことにより、押出成型直後のアルミニ
ウム合金と比較して、はるかに硬度の高いアルミ
ニウム合金に下地模様を付与することができる。
従つて、該アルミニウム合金に下地模様を付与す
る際にゆがみ、形状不良等の変形が生じることが
ないので、作業性が極めて良好となる。 Furthermore, since we employ a two-step age hardening process, mechanical strength, especially hardness, is imparted to the aluminum alloy before anodizing or forming a colored film.
It can be done completely in a series of steps. Moreover, by introducing the base pattern forming step between the two-stage age hardening treatment, it is possible to provide a base pattern to an aluminum alloy that is much harder than an aluminum alloy immediately after extrusion molding.
Therefore, when applying the base pattern to the aluminum alloy, no deformation such as distortion or defective shape occurs, resulting in extremely good workability.
また、下地模様がそのまま着色コントラスト模
様として表出するため、表面処理工程のラツキン
グ形態は横吊り及び縦吊りのいずれでもよく、特
に新しい技術を付加しなければならない要素もな
く、現在標準化されている方法でも充分対処でき
るという利点がある。 In addition, since the underlying pattern appears as a colored contrast pattern, the latching form in the surface treatment process can be either horizontal or vertical, and there is no need to add any new technology, which is currently standardized. This method has the advantage of being sufficient to deal with the problem.
さらに、本発明に従つて処理したアルミニウム
合金形材は、下地模様付与によつても性能低下は
全くなく、顕微鏡による酸化皮膜あるいは着色皮
膜の観察によつても欠陥は全く認められず、各種
試験においても電解着色による着色形材と何ら変
わらず、同用途、すなわち内外装の限定なく自由
に選択使用できる。 Furthermore, the aluminum alloy shapes treated according to the present invention showed no deterioration in performance even after being given a base pattern, no defects were observed when observing the oxide film or colored film under a microscope, and various tests were conducted. It is no different from colored shapes produced by electrolytic coloring, and can be freely selected and used for the same purpose, without any restrictions on interior or exterior use.
実施例
実施例 １
押出成型後のアルミニウム合金（Ａ―6063S）
形材を、160℃×3hrの条件で一次不完全時効硬化
処理した直後の高温状態に凹凸状のカーボンを接
触させて下地模様を形成し、該アルミニウム合金
形材を一旦常温まで冷却し、続いて190℃×3hrの
条件で２次時効硬化処理を施した。しかる後、該
アルミニウム合金形材を脱脂、エツチング、スマ
ツト除去し、常法により18W／Ｖ％の硫酸水溶液
中に浸漬して、電流密度1.1A／ｄm2（電圧約
12V）、液温20℃、30分の条件で陽極酸化処理を
行ない、その表面に約10μｍの陽極酸化皮膜を形
成した。次に水洗し、さらに着色処理として、長
さ200mm、幅150mm、高さ150mmの容器でカーボン
対極を容器の一方端に置いたものを電解着色用装
置として用い、長さ150mm、幅70mm、長さ1.3mmの
前記アルミニウム合金形材を極間距離180mmにし
て、下記の組成から成る液温16℃の電解液中に浸
漬して、初期電流密度1A／ｄm2、10Vの以加電圧
で５分交流電解したところ、前記下地模様部分が
背景に比較して濃いめに着色され、きれいな黄土
色の装飾模様が表出した。Examples Example 1 Aluminum alloy after extrusion molding (A-6063S)
Immediately after the shape was subjected to a primary incomplete age hardening treatment under the conditions of 160℃ x 3 hours, a base pattern was formed by contacting uneven carbon in the high temperature state, and the aluminum alloy shape was once cooled to room temperature, and then A secondary age hardening treatment was performed at 190°C for 3 hours. Thereafter, the aluminum alloy profile was degreased, etched, and smutted, and immersed in a 18 W/V% aqueous sulfuric acid solution using a conventional method to reduce the current density to 1.1 A/dm 2 (voltage approx.
12V), liquid temperature 20°C, and 30 minutes to form an anodized film of approximately 10 μm on the surface. Next, it was washed with water, and as a coloring treatment, a container with a length of 200 mm, a width of 150 mm, and a height of 150 mm was used as an electrolytic coloring device with a carbon counter electrode placed at one end of the container. The aluminum alloy profile with a diameter of 1.3 mm was set to a distance of 180 mm between the electrodes, and immersed in an electrolytic solution having the following composition at a temperature of 16°C. When fractional current electrolysis was carried out, the base pattern portion was colored darker than the background, and a beautiful ocher decorative pattern was exposed.
電解液浴組成：硫 酸 40ｇ／
三チオン酸ナトリウム １ｇ／
硫酸第１錫 ４ｇ／
実施例 ２
押出成形後のアルミニウム合金（Ａ―6063S）
形材を170℃×2hrの条件で一次不完全時効硬化処
理し、自然冷却させた。その後、該アルミニウム
合金形材表面に、高圧噴射装置を使用して、1200
Kg／cm2の水を噴射せしめて下地模様を形成し、次
いで、190℃×4hrの条件で２次時効硬化処理し
た。しかる後、該アルミニウム合金形材を脱脂、
エツチング、スマツト除去し、次に19W／Ｖ％の
硫酸水溶液中に浸漬し、電流密度1.2A／ｄm2
（電圧約12.5V）、液温21℃、35分間の条件で、陽
極酸化処理して、約11μｍの陽極酸化皮膜を形成
した。続いて、酸化皮膜改質処理として、前記陽
極酸化処理浴と同濃度、同温度条件にて、対極カ
ーボンにて、電流密度2.8A／ｄm2（電圧約
7.8V）で７分間交流電解を行ない、その後着色
処理として、実施例１と同様な装置を使用し、下
記の組成からなる液温20℃の電解液中に浸漬し
て、15Vの印加電圧で２分間、該アルミニウム合
金形材を陰極にして直流電解したところ、前記下
地模様部分が背景に比較してかなり濃いめに着色
され、鮮明なブロンズ色の装飾模様が表出した。Electrolyte bath composition: sulfuric acid 40g/sodium trithionate 1g/stannic sulfate 4g/Example 2 Aluminum alloy after extrusion molding (A-6063S)
The shapes were subjected to primary incomplete age hardening treatment at 170°C for 2 hours and allowed to cool naturally. After that, a high-pressure injection device was used to inject 1200
A base pattern was formed by spraying Kg/cm 2 of water, and then a secondary age hardening treatment was performed at 190° C. for 4 hours. After that, the aluminum alloy shape is degreased,
Etched and smut removed, then immersed in a 19 W/V% sulfuric acid aqueous solution, with a current density of 1.2 A/dm 2
(Voltage of about 12.5 V), liquid temperature of 21° C., and anodizing treatment for 35 minutes to form an anodic oxide film of about 11 μm. Next, as an oxide film modification treatment, a current density of 2.8 A/dm 2 (voltage approx.
7.8V) for 7 minutes, and then for coloring treatment, using the same device as in Example 1, immersing it in an electrolytic solution with the following composition at a temperature of 20°C, and applying an applied voltage of 15V. When DC electrolysis was carried out for 2 minutes using the aluminum alloy shape as a cathode, the base pattern was colored much darker than the background, and a clear bronze-colored decorative pattern appeared.
電解液組成：硫酸ニツケル 30ｇ／
硼 酸 20ｇ／
硫酸アンモニウム 15ｇ／
PH4.5
実施例 ３
実施例２の酸化皮膜改質処理を、電解密度
1A／ｄm2（電圧約5V）で２分間アルミニウム合
金形材を陰極に接続して直流電解した以外は、実
施例２と全く同じ方法で前記アルミニウム合金形
材を処理したところ、該形材表面の下地模様部分
と背景との間に濃淡差のあるきれいなブロンズ色
の装飾模様が表出した。Electrolyte composition: Nickel sulfate 30g/boric acid 20g/ammonium sulfate 15g/PH4.5 Example 3 The oxide film modification treatment of Example 2 was carried out by changing the electrolytic density.
The aluminum alloy profile was treated in exactly the same manner as in Example 2, except that the aluminum alloy profile was connected to the cathode and subjected to DC electrolysis at 1A/dm 2 (voltage approximately 5V) for 2 minutes. A beautiful bronze-colored decorative pattern with a difference in shading between the base pattern and the background appeared.
実施例 ４
押出成型後のアルミニウム合金（Ａ―6063S）
形材を160℃×3hrの条件で１次不完全時効硬化処
理し、常温まで冷却した後、該アルミニウム合金
形材表面に、10mm／secの速度にて、周波数3.0K
Hz、16Aのレーザー光線を照射して下地模様を形
成した。次いで、190℃×3hrの条件で２次時効硬
化処理し、しかる後、該アルミニウム合金形材を
脱脂、エツチング、スマツト除去し、該形材を
18W／Ｖ％の硫酸水溶液中に浸漬し、電流密度
1.1A／ｄm2（電圧約12V）、液温20℃、時間30分
の条件で陽極酸化し、約10μｍの陽極酸化皮膜を
形成した。次に、着色処理として、実施例１と同
様な装置を使用し、下記の組成を有する浴温20℃
の電解液中に浸漬して、初期電流密度1A／ｄ
m2、11Vの印加電圧で５分30秒交流電解したとこ
ろ、下地模様部分が背景に比較してかなり濃く着
色して鮮明なオリーブ色の装飾模様となつた。Example 4 Aluminum alloy after extrusion molding (A-6063S)
After subjecting the shape to incomplete age hardening at 160°C for 3 hours and cooling it to room temperature, the surface of the aluminum alloy shape was heated at a frequency of 3.0K at a speed of 10mm/sec.
A base pattern was formed by irradiating a laser beam of 16A at Hz. Next, the aluminum alloy shape is subjected to a secondary age hardening treatment at 190°C for 3 hours, and then the aluminum alloy shape is degreased, etched, and smut removed.
Immersed in 18W/V% sulfuric acid aqueous solution, current density
Anodizing was carried out under the conditions of 1.1 A/dm 2 (voltage of about 12 V), liquid temperature of 20° C., and time of 30 minutes to form an anodic oxide film of about 10 μm. Next, as a coloring treatment, using the same apparatus as in Example 1, a bath having the following composition at a temperature of 20°C.
The initial current density is 1A/d.
When alternating current electrolysis was carried out for 5 minutes and 30 seconds at an applied voltage of m 2 and 11 V, the underlying pattern was colored much darker than the background, resulting in a clear olive-colored decorative pattern.
電解液組成：硫 酸 20ml／
硫酸ニツケル 30ｇ／
硫酸第１錫 ５ｇ／
クレゾールスルフオン酸 10ｇ／
実施例 ５
押出成型後自然冷却したアルミニウム合金（Ａ
―6063S）形材を160℃×3hrの条件で一次不完全
時効硬化処理し、常温にまで冷却した。次に、該
アルミニウム合金形材表面に凹凸状のカーボンを
接触させ、下地模様を形成し、さらに200℃×2hr
の条件で２次時効硬化処理した。しかる後、該ア
ルミニウム合金形材を脱脂、エツチング、スマツ
ト除去し、次に陽極酸化処理として、長さ200
mm、幅150mm、高さ150mmの容器でカーボン対極を
容器の一方端に置いたものを陽極酸化処理装置し
て用い、下記の組成を有する浴温20℃の電解液中
に浸漬して、電流密度2A／ｄm2、7Vの印加電圧
で45分交流電解したところ、下地模様部分が背景
に比較してかなり濃く着色して鮮明なオリーブ色
の装飾模様となつた。Electrolyte composition: sulfuric acid 20ml/nickel sulfate 30g/stannic sulfate 5g/cresol sulfonic acid 10g/Example 5 Aluminum alloy (A) naturally cooled after extrusion molding
-6063S) The shape was subjected to primary incomplete age hardening treatment at 160℃ x 3 hours, and then cooled to room temperature. Next, uneven carbon was brought into contact with the surface of the aluminum alloy shape to form a base pattern, and further heated at 200°C for 2 hours.
A secondary age hardening treatment was performed under the following conditions. After that, the aluminum alloy profile was degreased, etched, and smutted, and then anodized to a length of 200 mm.
A container with dimensions of 150 mm, width 150 mm, and height 150 mm, with a carbon counter electrode placed at one end of the container, was used as an anodizing treatment device. When AC electrolysis was carried out for 45 minutes at a density of 2 A/dm 2 and an applied voltage of 7 V, the underlying pattern was colored much darker than the background, resulting in a clear olive-colored decorative pattern.
電解液組成：硫 酸 18W／Ｖ％
硫酸第１錫： ２ｇ／
実施例 ６
実施例２の下地模様形成処理に代えて、肉厚約
0.1mmのステンレス板を食刻して約30μｍの凹凸
のある模様状エンボス版を作り、これを模様形成
面が形材と密接するようにアルミニウム合金形材
上に載置し、その上からローラーにて圧刻して、
該アルミニウム合金表面に下地模様を形成した以
外は、実施例２と全く同じ方法にて前記アルミニ
ウム合金形材を処理したところ、該形材表面に下
地模様部分と背景との間に濃淡差のあるきれいな
装飾模様を表出した。Electrolyte composition: Sulfuric acid 18W/V% Stannous sulfate: 2g/Example 6 Instead of the base pattern forming treatment of Example 2, a wall thickness of approx.
A 0.1 mm stainless steel plate is etched to create a patterned embossed plate with irregularities of approximately 30 μm. This is placed on an aluminum alloy profile so that the patterned surface is in close contact with the profile, and then a roller is placed over it. stamped with
When the aluminum alloy profile was treated in exactly the same manner as in Example 2, except that a base pattern was formed on the surface of the aluminum alloy, there was a difference in shading between the base pattern and the background on the surface of the profile. It has a beautiful decorative pattern.
実施例 ７
押出成型後のアルミニウム合金（Ａ―6063S）
形材を180℃×1hrの条件で一次不完全時効硬化処
理し、常温まで冷却した後、ステンレスセツトワ
イヤー（粒度100）を6.4mmφのノズルより空気圧
２Kg／cm2で噴射して下地模様を形成し、次いで該
アルミニウム合金形材を200℃×2hrの条件で２次
時効硬化処理し、しかる後に実施例３と同様に脱
脂、エツチング、スマツト除去し、該形材を
17W／Ｖ％の硫酸水溶液中に浸漬し、電流密度
1.2A／ｄm2（電圧約12.5V）、液温20℃、時間35
分の条件で陽極酸化し、約10.5μｍの陽極酸化皮
膜を形成した。つぎに、酸化皮膜改質処理とし
て、電流密度1.2A／ｄm2（電圧約6V）で１分30
秒アルミニウム合金形材を陰極に接続して直流電
解した。次に、着色処理として実施例１と同じ容
器にて、下記の組成を有する浴温28℃の電解液中
に浸漬して、初期電流密度1A／ｄm2、11Vの印加
電圧で３分交流電解したところ、サンドブラスト
を当てた面のみが黒茶色となり、一方、サンドブ
ラストを当てない面は淡茶色となり、形材の面に
より着色の異なる美しい形材となつた。Example 7 Aluminum alloy after extrusion molding (A-6063S)
After subjecting the shape to incomplete age hardening at 180℃ x 1hr and cooling it to room temperature, a base pattern is formed by spraying stainless steel set wire (grain size 100) at an air pressure of 2Kg/cm 2 from a 6.4mmφ nozzle. Then, the aluminum alloy shape was subjected to a secondary age hardening treatment at 200°C x 2 hours, and then degreased, etched, and smut removed in the same manner as in Example 3, and the shape was
Immersed in 17W/V% sulfuric acid aqueous solution, current density
1.2A/dm 2 (voltage approx. 12.5V), liquid temperature 20℃, time 35
Anodic oxidation was performed under conditions of 10 minutes to form an anodic oxide film of approximately 10.5 μm. Next, as an oxide film modification treatment, the current density was 1.2A/dm 2 (voltage approximately 6V) for 1 minute 30 minutes.
A second aluminum alloy profile was connected to the cathode for direct current electrolysis. Next, as a coloring treatment, the same container as in Example 1 was immersed in an electrolytic solution having the following composition at a bath temperature of 28°C, and AC electrolysis was carried out for 3 minutes at an initial current density of 1 A/dm 2 and an applied voltage of 11 V. As a result, only the sandblasted side became blackish brown, while the non-sandblasted side became light brown, resulting in a beautiful shape with different colors depending on the side of the shape.
電解液組成：硫酸ニツケル 25ｇ／
硫酸マグネシウム 15ｇ／
硫酸アンモニウム 30ｇ／
硼 酸 20ｇ／
チオ硫酸アンモニウム １ｇ／
PH 5.5
比較例 １
実施例１において、時効硬化処理を１次不完全
時効160℃×3hrの条件のみとした以外は、実施例
１と同様の処理をしたところ、淡黄土色となり、
下地模様部分が背景と比べわずかに濃く着色され
たが、実施例１に比べ不鮮明であつて、およそ模
様と呼ぶにはかけ離れたものであり、またビツカ
ース硬度も低かつた。Electrolyte composition: Nickel sulfate 25g/Magnesium sulfate 15g/Ammonium sulfate 30g/Boric acid 20g/Ammonium thiosulfate 1g/PH 5.5 Comparative example 1 In Example 1, the age hardening treatment was performed only under the conditions of primary incomplete aging at 160°C x 3 hours. When the same treatment as in Example 1 was carried out except for
Although the underlying pattern was colored slightly darker than the background, it was less clear than in Example 1 and could hardly be called a pattern, and the Vickers hardness was also low.
ビツカース硬度：
実施例１ 80.9
比較例１ 66.5
比較例 ２
実施例１において、１次時効硬化処理を190℃
×6hrの完全時効硬化処理とした以外は、実施例
１と同様の処理をしたところ、全面が黄土色に着
色され、下地模様部分と背景との着色差はなく模
様を呈さなかつた。又ビツカース硬度も低かつ
た。Bitkers hardness: Example 1 80.9 Comparative example 1 66.5 Comparative example 2 In Example 1, the primary age hardening treatment was performed at 190°C.
When the same treatment as in Example 1 was performed except that the complete age hardening treatment was performed for 6 hours, the entire surface was colored ocher, and there was no difference in coloring between the base pattern and the background, and no pattern was exhibited. Also, the Bitkers hardness was low.
ビツカース硬度： 実施例１ 80.9 比較例２ 74.5Bitkers hardness: Example 1 80.9 Comparative example 2 74.5
第１図はアルミニウム合金（Ａ―6063S）の硬
度に及ぼす時効硬化処理と処理時間の影響を示す
グラフ、第２図は２段階時効硬化処理における１
次時効（160℃）と２次時効（190℃）の組合せ及
びその条件がアルミニウム合金（Ａ―6063S）の
硬度に及ぼす影響を示すグラフ、第３図は１次不
完全時効硬化処理の時間と温度の適正範囲を示す
グラフである。
Figure 1 is a graph showing the effects of age hardening treatment and treatment time on the hardness of aluminum alloy (A-6063S), and Figure 2 is a graph showing the effects of age hardening treatment and treatment time on the hardness of aluminum alloy (A-6063S).
A graph showing the effects of the combination of secondary aging (160°C) and secondary aging (190°C) and their conditions on the hardness of aluminum alloy (A-6063S). Figure 3 shows the time of primary incomplete age hardening treatment and It is a graph showing the appropriate range of temperature.
Claims (1)
完全時効硬化処理を施し、 (B) 次いで、該アルミニウム合金表面に機械的操
作による下地模様を施した後、 (C) 前記１次不完全時効硬化処理の処理温度より
高い温度条件で２次不完全時効硬化処理乃至完
全時効硬化処理を施し、 (D) しかる後、前記アルミニウム合金表面に着色
皮膜を形成する ことにより、前記下地模様をアルミニウム合金表
面に鮮明に表出させることを特徴とするアルミニ
ウム合金の模様付け表面処理方法。 ２ (A) 押出成型後のアルミニウム合金に１次不
完全時効硬化処理を施し、 (B) 次いで、該アルミニウム合金表面に機械的操
作による下地模様を施した後、 (C) 前記１次不完全時効硬化処理の処理温度より
高い温度条件で２次不完全時効硬化処理乃至完
全時効硬化処理を施し、 (D′) しかる後、 (i) 前記アルミニウム合金に常法による陽極酸
化皮膜を形成し、 (ii) 続いて無機酸及び／又は有機酸浴中で交流
電解して前記陽極酸化皮膜を二重皮膜構造に
改質した後、 (iii) 該皮膜に着色処理を施す ことにより、前記下地模様をアルミニウム合金表
面に鮮明に表出させることを特徴とするアルミニ
ウム合金の模様付け表面処理方法。 ３ (A) 押出成型後のアルミニウム合金に１次不
完全時効硬化処理を施し、 (B) 次いで、該アルミニウム合金表面に機械的操
作による下地模様を施した後、 (C) 前記１次不完全時効硬化処理の処理温度より
高い温度条件で２次不完全時効硬化処理乃至完
全時効硬化処理を施し、 (D″) しかる後、 (i) 前記アルミニウム合金に常法による陽極酸
化皮膜を形成し、 (ii) 続いて無機酸及び／又は有機酸浴中で前記
アルミニウム合金を陰極に接続して直流電解
することによつて前記陽極酸化皮膜を改質し
た後、 (iii) 該皮膜に着色処理を施す ことにより、前記下地模様をアルミニウム合金表
面に鮮明に表出させることを特徴とするアルミニ
ウム合金の模様付け表面処理方法。[Claims] 1. (A) A primary incomplete age hardening treatment is applied to the aluminum alloy after extrusion molding, (B) Next, a base pattern is applied to the surface of the aluminum alloy by mechanical operation, (C ) Performing a secondary incomplete age hardening treatment or complete age hardening treatment at a temperature higher than the treatment temperature of the first incomplete age hardening treatment, (D) After that, by forming a colored film on the surface of the aluminum alloy. . A method for patterning and surface treatment of aluminum alloys, characterized in that the base pattern is clearly exposed on the surface of the aluminum alloy. 2 (A) The aluminum alloy after extrusion molding is subjected to a primary incomplete age hardening treatment, (B) The aluminum alloy surface is then subjected to a base pattern by mechanical manipulation, and (C) the aforementioned primary imperfection is applied. Performing a secondary incomplete age hardening treatment or complete age hardening treatment at a temperature higher than the treatment temperature of the age hardening treatment, (D') After that, (i) forming an anodized film on the aluminum alloy by a conventional method, (ii) Subsequently, the anodic oxide film is modified into a double film structure by alternating current electrolysis in an inorganic acid and/or organic acid bath, and (iii) the film is colored to form the base pattern. A method for treating the patterned surface of an aluminum alloy, which is characterized by clearly displaying the pattern on the surface of the aluminum alloy. 3 (A) Performing a primary incomplete age hardening treatment on the aluminum alloy after extrusion molding, (B) Next, applying a base pattern to the surface of the aluminum alloy by mechanical manipulation, (C) The above-mentioned primary imperfection Performing a secondary incomplete age hardening treatment or complete age hardening treatment at a temperature higher than the treatment temperature of the age hardening treatment, (D″) After that, (i) forming an anodized film on the aluminum alloy by a conventional method, (ii) Subsequently, the aluminum alloy is connected to a cathode in an inorganic acid and/or organic acid bath and the anodic oxide film is modified by direct current electrolysis, and (iii) the film is colored. A patterning surface treatment method for an aluminum alloy, characterized in that the base pattern is clearly exposed on the surface of the aluminum alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10574783A JPS59232294A (en) | 1983-06-15 | 1983-06-15 | Surface treatment for patterning of aluminum alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10574783A JPS59232294A (en) | 1983-06-15 | 1983-06-15 | Surface treatment for patterning of aluminum alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59232294A JPS59232294A (en) | 1984-12-27 |
| JPS6259193B2 true JPS6259193B2 (en) | 1987-12-09 |
Family
ID=14415843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10574783A Granted JPS59232294A (en) | 1983-06-15 | 1983-06-15 | Surface treatment for patterning of aluminum alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59232294A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61183497A (en) * | 1985-02-06 | 1986-08-16 | Yoshida Kogyo Kk <Ykk> | Surface treatment for patterning of aluminum alloy |
-
1983
- 1983-06-15 JP JP10574783A patent/JPS59232294A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59232294A (en) | 1984-12-27 |
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