JP2022014297A - Metal coloring solution for chemical conversion and method for coloring metal - Google Patents
Metal coloring solution for chemical conversion and method for coloring metal Download PDFInfo
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- JP2022014297A JP2022014297A JP2020116562A JP2020116562A JP2022014297A JP 2022014297 A JP2022014297 A JP 2022014297A JP 2020116562 A JP2020116562 A JP 2020116562A JP 2020116562 A JP2020116562 A JP 2020116562A JP 2022014297 A JP2022014297 A JP 2022014297A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 176
- 239000002184 metal Substances 0.000 title claims abstract description 176
- 238000004040 coloring Methods 0.000 title claims abstract description 108
- 239000000126 substance Substances 0.000 title claims abstract description 88
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 87
- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 65
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 19
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- 239000010452 phosphate Substances 0.000 claims abstract description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 18
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 239000011701 zinc Substances 0.000 claims abstract description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 6
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 4
- SIWNEELMSUHJGO-UHFFFAOYSA-N 2-(4-bromophenyl)-4,5,6,7-tetrahydro-[1,3]oxazolo[4,5-c]pyridine Chemical compound C1=CC(Br)=CC=C1C(O1)=NC2=C1CCNC2 SIWNEELMSUHJGO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 76
- 150000004715 keto acids Chemical class 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 14
- 239000003086 colorant Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 8
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims description 7
- 229940005991 chloric acid Drugs 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical group [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims description 3
- 239000002253 acid Substances 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 description 46
- 235000019646 color tone Nutrition 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000012736 aqueous medium Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- -1 fluororesin Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/23—Condensed phosphates
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
本発明は、化成処理用金属着色液及び金属着色処理方法に関する。 The present invention relates to a metal coloring liquid for chemical conversion treatment and a metal coloring treatment method.
従来、種々の金属、特にアルミニウム又はアルミニウム合金の着色において、黄色～茶色系の色調を得るには陽極酸化や陽極酸化皮膜に染料を吸着させる方法が一般的である。 Conventionally, in coloring of various metals, particularly aluminum or an aluminum alloy, a method of anodizing or adsorbing a dye on an anodized film is generally used to obtain a yellow to brownish color tone.
例えば、特許文献１には、アルミニウム又はアルミニウム合金の素地表面に形成した電解発色又は自然発色による発色皮膜を、電解着色可能な皮膜構造とした後、電解着色を行って、色を重ね合わせて新たな色調の皮膜を得ることを特徴とするアルミニウム及びアルミニウム合金の電解着色方法が開示されている。そして、このような構成によれば、従来の電解着色方法では得られない様々な中間色を含む種々の色調を得ることができる電解着色方法を提供することができる、と記載されている。 For example, in Patent Document 1, a color-developing film formed on the surface of an aluminum or aluminum alloy substrate by electrolytic coloring or natural coloring is formed into a film structure capable of electrolytic coloring, and then electrolytic coloring is performed to superimpose the colors. A method for electrolytically coloring aluminum and an aluminum alloy, which is characterized by obtaining a film having a different color tone, is disclosed. Further, it is described that according to such a configuration, it is possible to provide an electrolytic coloring method capable of obtaining various color tones including various neutral colors which cannot be obtained by the conventional electrolytic coloring method.
しかしながら、従来、金属表面を黄色～茶色系の色調に着色するには、例えば、アルミニウム又はアルミニウム合金であればアルマイトを利用する必要があった。すなわち、金属表面を黄色～茶色系の色調に着色するには、酸化膜を表面に有する金属を利用する必要があり、処理工程が多く、処理効率の改善が望まれている。 However, conventionally, in order to color the metal surface in a yellow to brownish color tone, for example, in the case of aluminum or an aluminum alloy, it has been necessary to use alumite. That is, in order to color the metal surface in a yellow to brownish color tone, it is necessary to use a metal having an oxide film on the surface, and there are many treatment steps, and improvement in treatment efficiency is desired.
また、特許文献２には、アルミニウム又はアルミニウム合金の表面を金色に着色する処理剤について開示しているが、金属表面を化成処理によって黄色～茶色系の色調に着色するには更なる研究・開発の余地があった。 Further, Patent Document 2 discloses a treatment agent for coloring the surface of aluminum or an aluminum alloy in gold, but further research and development for coloring the metal surface to a yellow to brown color by chemical conversion treatment. There was room for.
本発明は、このような問題に鑑み、良好な処理効率で金属表面を黄色～茶色系の色調に着色することが可能な化成処理用金属着色液及び金属着色処理方法を提供することを目的とする。 In view of such problems, it is an object of the present invention to provide a metal coloring liquid for chemical conversion treatment and a metal coloring treatment method capable of coloring a metal surface in a yellow to brownish color tone with good treatment efficiency. do.
本発明者らは上記課題を解決するために鋭意検討した結果、過マンガン酸若しくはその塩と、無機酸及びその塩のいずれか一方又は両方と、縮合リン酸塩とを含む化成処理用金属着色液により処理を行うことで、良好な処理効率で金属表面を黄色～茶色系の色調に着色することが可能となることを見出した。 As a result of diligent studies to solve the above problems, the present inventors have colored a metal for chemical conversion treatment containing permanganic acid or a salt thereof, one or both of an inorganic acid and a salt thereof, and a condensed phosphate. It has been found that the treatment with a liquid makes it possible to color the metal surface in a yellow to brownish color with good treatment efficiency.
以上の知見を基礎として完成した本発明は一側面において、過マンガン酸若しくはその塩と、無機酸及びその塩のいずれか一方又は両方と、縮合リン酸塩とを含む化成処理用金属着色液である。 The present invention completed on the basis of the above findings is, in one aspect, a metal coloring liquid for chemical conversion treatment containing permanganic acid or a salt thereof, one or both of an inorganic acid and a salt thereof, and a condensed phosphate. be.
本発明の化成処理用金属着色液は一実施形態において、前記過マンガン酸若しくはその塩が、過マンガン酸、過マンガン酸ナトリウム、過マンガン酸カリウム、過マンガン酸亜鉛、過マンガン酸マグネシウム、過マンガン酸カルシウム、過マンガン酸アンモニウム、又はこれらの組み合わせである。 In one embodiment of the metal coloring liquid for chemical conversion of the present invention, the permanganate or a salt thereof is permanganate, sodium permanganate, potassium permanganate, zinc permanganate, magnesium permanganate, permanganate. Calcium acid, ammonium permanganate, or a combination thereof.
本発明の化成処理用金属着色液は別の一実施形態において、前記無機酸及びその塩が、リン酸、硫酸、硝酸、炭酸、塩酸、及びこれらの塩、又はこれらの組み合わせである。 In another embodiment of the metal coloring liquid for chemical conversion treatment of the present invention, the inorganic acid and a salt thereof are phosphoric acid, sulfuric acid, nitric acid, carbonic acid, hydrochloric acid, salts thereof, or a combination thereof.
本発明の化成処理用金属着色液は更に別の一実施形態において、前記縮合リン酸塩が、ピロリン酸カリウム、トリポリリン酸ナトリウム、又はこれらの組み合わせである。 In still another embodiment of the metal coloring liquid for chemical conversion treatment of the present invention, the condensed phosphate is potassium pyrophosphate, sodium tripolyphosphate, or a combination thereof.
本発明の化成処理用金属着色液は更に別の一実施形態において、前記過マンガン酸若しくはその塩の含有量が、０．５～５０ｇ／Ｌである。 In still another embodiment, the metal coloring liquid for chemical conversion treatment of the present invention has a content of the permanganate or a salt thereof of 0.5 to 50 g / L.
本発明の化成処理用金属着色液は更に別の一実施形態において、前記無機酸及びその塩の含有量が、０．５～１００ｇ／Ｌである。 In still another embodiment, the metal coloring liquid for chemical conversion treatment of the present invention has a content of the inorganic acid and a salt thereof of 0.5 to 100 g / L.
本発明の化成処理用金属着色液は更に別の一実施形態において、前記縮合リン酸塩の含有量が、１～１５０ｇ／Ｌである。 In still another embodiment, the metal coloring liquid for chemical conversion treatment of the present invention has a content of the condensed phosphate of 1 to 150 g / L.
本発明の化成処理用金属着色液は更に別の一実施形態において、更に、オキソ酸若しくはその塩を含む。 In still another embodiment, the metal colorant for chemical conversion treatment of the present invention further contains an oxoacid or a salt thereof.
本発明の化成処理用金属着色液は更に別の一実施形態において、前記オキソ酸若しくはその塩が、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、ホウ酸、若しくはこれらの塩、又はこれらの組み合わせである。 In still another embodiment of the metal coloring liquid for chemical conversion of the present invention, the oxoacid or a salt thereof is perchloric acid, chloric acid, chloric acid, hypochloric acid, bromic acid, boric acid, or these. Salt, or a combination thereof.
本発明の化成処理用金属着色液は更に別の一実施形態において、前記オキソ酸若しくはその塩の合計含有量が、０．５～１００ｇ／Ｌである。 In still another embodiment, the metal coloring liquid for chemical conversion treatment of the present invention has a total content of the oxoacid or a salt thereof of 0.5 to 100 g / L.
本発明の化成処理用金属着色液は更に別の一実施形態において、処理対象の金属が、アルミニウム、アルミニウム合金、銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、マグネシウム、及びマグネシウム合金からなる群から選択される少なくとも１種である。 In still another embodiment, the metal coloring liquid for chemical conversion of the present invention comprises a metal to be treated from aluminum, an aluminum alloy, copper, a copper alloy, iron, an iron alloy, zinc, a zinc alloy, magnesium, and a magnesium alloy. At least one selected from the group of
本発明は別の一側面において、本発明の化成処理用金属着色液を使用して、金属に対して化成処理によって着色を行う工程を含む金属着色処理方法である。 In another aspect, the present invention is a metal coloring treatment method including a step of coloring a metal by chemical conversion treatment using the metal coloring liquid for chemical conversion treatment of the present invention.
本発明の金属着色処理方法は一実施形態において、前記金属に対して化成処理によって着色を行う工程において、前記金属を前記化成処理用金属着色液に１０℃～８０℃で３０秒～２０分間浸漬することで前記金属を着色する。 In one embodiment, the metal coloring treatment method of the present invention immerses the metal in the metal coloring liquid for chemical conversion treatment at 10 ° C. to 80 ° C. for 30 seconds to 20 minutes in the step of coloring the metal by chemical conversion treatment. By doing so, the metal is colored.
本発明によれば、良好な処理効率で金属表面を黄色～茶色系の色調に着色することが可能な化成処理用金属着色液及び金属着色処理方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a metal coloring liquid for chemical conversion treatment and a metal coloring treatment method capable of coloring a metal surface in a yellow to brownish color tone with good treatment efficiency.
以下、本発明の化成処理用金属着色液及び金属着色処理方法の実施形態について説明するが、本発明は、これに限定されて解釈されるものではなく、本発明の範囲を逸脱しない限りにおいて、当業者の知識に基づいて、種々の変更、修正、改良を加え得るものである。 Hereinafter, embodiments of the metal coloring liquid for chemical conversion treatment and the metal coloring treatment method of the present invention will be described, but the present invention is not limited to this and is not construed as long as it does not deviate from the scope of the present invention. Various changes, modifications and improvements can be made based on the knowledge of those skilled in the art.
〔化成処理用金属着色液〕
本発明の実施形態に係る化成処理用金属着色液は、過マンガン酸若しくはその塩と、無機酸及びその塩のいずれか一方又は両方と、縮合リン酸塩とを含む。過マンガン酸若しくはその塩と、無機酸及びその塩のいずれか一方又は両方と、縮合リン酸塩とを含む化成処理用金属着色液を用いることで、処理対象の金属を当該化成処理用金属着色液に浸漬するだけで、金属表面に皮膜（着色皮膜）を形成することができ、これにより黄色～茶色系の色調に着色することができる。このため、金属表面を黄色～茶色系の色調に着色する際に、当該金属の表面に酸化膜を形成しておく必要もなく、電解によって着色する必要もなくなり、処理効率が良好となる。また、本発明の実施形態に係る化成処理用金属着色液によれば、金属表面に形成する皮膜（着色皮膜）の密着性も良好となる。
[Metal coloring liquid for chemical conversion treatment]
The metal coloring liquid for chemical treatment according to the embodiment of the present invention contains permanganic acid or a salt thereof, one or both of an inorganic acid and a salt thereof, and a condensed phosphate. By using a metal coloring liquid for chemical conversion treatment containing permanganic acid or a salt thereof, one or both of an inorganic acid and a salt thereof, and a condensed phosphate, the metal to be treated is colored with the metal for chemical conversion treatment. A film (colored film) can be formed on the metal surface simply by immersing it in the liquid, whereby it is possible to color the metal in a yellow to brownish hue. Therefore, when the metal surface is colored in a yellow to brownish color tone, it is not necessary to form an oxide film on the surface of the metal, and it is not necessary to color the metal surface by electrolysis, so that the treatment efficiency is improved. Further, according to the metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention, the adhesion of the film (colored film) formed on the metal surface is also good.
（処理対象の金属）
本発明の実施形態に係る化成処理用金属着色液で表面を着色する対象となる金属（処理対象の金属）としては、アルミニウム、アルミニウム合金、銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金、マグネシウム、及びマグネシウム合金からなる群から選択される少なくとも１種が挙げられる。処理対象の金属は、当該金属自体であってもよく、例えば、鉄系材料や鉄系部品などの金属基材の表面に形成された、当該金属のメッキであってもよい。
(Metal to be processed)
Examples of the metal (metal to be treated) whose surface is to be colored with the chemical coloring liquid according to the embodiment of the present invention include aluminum, aluminum alloy, copper, copper alloy, iron, iron alloy, zinc, and zinc alloy. , Magnesium, and at least one selected from the group consisting of magnesium alloys. The metal to be treated may be the metal itself, or may be, for example, plating of the metal formed on the surface of a metal base material such as an iron-based material or an iron-based component.
（過マンガン酸若しくはその塩）
過マンガン酸若しくはその塩としては、過マンガン酸、過マンガン酸ナトリウム、過マンガン酸カリウム、過マンガン酸亜鉛、過マンガン酸マグネシウム、過マンガン酸カルシウム、過マンガン酸アンモニウム、又はこれらの組み合わせを用いることができる。また、過マンガン酸若しくはその塩としては、過マンガン酸ナトリウム、過マンガン酸カリウムがより好ましい。
(Potassium permanganate or its salt)
As permanganate or a salt thereof, permanganate, sodium permanganate, potassium permanganate, zinc permanganate, magnesium permanganate, calcium permanganate, ammonium permanganate, or a combination thereof shall be used. Can be done. Further, as the permanganate or a salt thereof, sodium permanganate and potassium permanganate are more preferable.
本発明の実施形態に係る化成処理用金属着色液における過マンガン酸若しくはその塩の含有量は、処理対象の金属の種類、及び、どの程度の黄色～茶色系の色調に着色するかによるが、例えば、０．５～５０ｇ／Ｌとすることができる。基本的には、過マンガン酸若しくはその塩の含有量が少ないほど、金属表面を薄い黄色～濃い黄色系の色調に着色することができる。また、過マンガン酸若しくはその塩の含有量が多いほど、金属表面を薄い茶色～濃い茶色系の色調に着色することができる。過マンガン酸若しくはその塩の含有量は、１～３０ｇ／Ｌであることがより好ましく、２～２０ｇ／Ｌであることがより好ましい。 The content of permanganate or a salt thereof in the metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention depends on the type of the metal to be treated and the degree of yellow to brown color tones. For example, it can be 0.5 to 50 g / L. Basically, the smaller the content of permanganate or a salt thereof, the more the metal surface can be colored in a light yellow to deep yellowish color tone. Further, the higher the content of permanganate or a salt thereof, the more the metal surface can be colored in a light brown to dark brown color tone. The content of permanganate or a salt thereof is more preferably 1 to 30 g / L, and more preferably 2 to 20 g / L.
本発明の実施形態に係る化成処理用金属着色液は、後述のように、オキソ酸若しくはその塩等を含んでもよいが、これらの成分を含まない化成処理用金属着色液の場合、特にアルミニウム、アルミニウム合金などの金属表面を、より美観に優れた黄色～茶色系の色調に着色することができる。 As described later, the metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention may contain oxo acid or a salt thereof, but in the case of the metal coloring liquid for chemical conversion treatment which does not contain these components, aluminum, in particular, The surface of a metal such as an aluminum alloy can be colored in a more aesthetically pleasing yellow to brownish hue.
（無機酸及びその塩）
無機酸及びその塩は、リン酸、硫酸、硝酸、炭酸、塩酸、及びこれらの塩、又はこれらの組み合わせであるのが好ましい。リン酸、硫酸、硝酸、炭酸、塩酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。また、無機酸及びその塩としては、リン酸三ナトリウム、硝酸、硝酸銅、塩化亜鉛がより好ましい。
(Inorganic acid and its salt)
The inorganic acid and its salt are preferably phosphoric acid, sulfuric acid, nitric acid, carbonic acid, hydrochloric acid, and salts thereof, or a combination thereof. As the salts of phosphoric acid, sulfuric acid, nitric acid, carbonic acid, and hydrochloric acid, these metal salts, ammonium salts, and the like can be used. Further, as the inorganic acid and its salt, trisodium phosphate, nitric acid, copper nitrate and zinc chloride are more preferable.
本発明の実施形態に係る化成処理用金属着色液における無機酸及びその塩の含有量は、処理対象の金属の種類、及び、どの程度の黄色～茶色系の色調に着色するかによるが、例えば、０．５～１００ｇ／Ｌとすることができる。基本的には、無機酸及びその塩の含有量が少ないほど、金属表面を薄い黄色～濃い黄色系の色調に着色することができる。また、無機酸及びその塩の含有量が多いほど、金属表面を薄い茶色～濃い茶色系の色調に着色することができる。無機酸及びその塩の含有量は、１～３０ｇ／Ｌであることがより好ましく、２～２０ｇ／Ｌであることがより好ましい。 The content of the inorganic acid and its salt in the metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention depends on the type of the metal to be treated and the degree of yellow to brown color tones, for example. , 0.5 to 100 g / L. Basically, the smaller the content of the inorganic acid and its salt, the more the metal surface can be colored in a light yellow to deep yellowish color tone. Further, as the content of the inorganic acid and the salt thereof increases, the metal surface can be colored in a light brown to dark brown color tone. The content of the inorganic acid and its salt is more preferably 1 to 30 g / L, and more preferably 2 to 20 g / L.
（縮合リン酸塩）
縮合リン酸塩は、ピロリン酸カリウム、トリポリリン酸ナトリウム、又はこれらの組み合わせであるのが好ましい。縮合リン酸塩の含有量は、処理対象の金属の種類、及び、どの程度の黄色～茶色系の色調に着色するかによるが、例えば、１～１５０ｇ／Ｌとすることができる。基本的には、縮合リン酸塩の含有量が少ないほど、金属表面を薄い黄色～濃い黄色系の色調に着色することができる。また、縮合リン酸塩が多いほど、金属表面を薄い茶色～濃い茶色系の色調に着色することができる。縮合リン酸塩は、３～５０ｇ／Ｌであることがより好ましく、４～４０ｇ／Ｌであることがより好ましい。
(Condensed phosphate)
The condensed phosphate is preferably potassium pyrophosphate, sodium tripolyphosphate, or a combination thereof. The content of the condensed phosphate depends on the type of the metal to be treated and the degree of yellow to brown color tones, and can be, for example, 1 to 150 g / L. Basically, the smaller the content of condensed phosphate, the lighter yellow to deeper yellowish the color of the metal surface can be. Further, the more the condensed phosphate is, the more the metal surface can be colored in a light brown to dark brown color tone. The condensed phosphate is more preferably 3 to 50 g / L, more preferably 4 to 40 g / L.
（オキソ酸若しくはその塩）
本発明の実施形態に係る化成処理用金属着色液は、更に、オキソ酸若しくはその塩を含んでもよい。本発明の実施形態に係る化成処理用金属着色液は、オキソ酸若しくはその塩を含んでも、良好な処理効率で前述の処理対象の金属表面を黄色～茶色系の色調に着色することができる。また、本発明の実施形態に係る化成処理用金属着色液は、オキソ酸若しくはその塩を含むことにより、特に銅、銅合金、鉄、鉄合金、亜鉛、亜鉛合金などの金属の表面を、より美観に優れた黄色～茶色系の色調に着色することができる。
(Oxyacid or its salt)
The metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention may further contain oxoacid or a salt thereof. Even if the metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention contains oxoacid or a salt thereof, the metal surface to be treated can be colored in a yellow to brown color tone with good treatment efficiency. Further, the metal coloring liquid for chemical conversion according to the embodiment of the present invention contains oxoacid or a salt thereof, so that the surface of a metal such as copper, copper alloy, iron, iron alloy, zinc, zinc alloy, etc. can be further improved. It can be colored in yellow to brown tones with excellent aesthetics.
オキソ酸若しくはその塩が、過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、ホウ酸、若しくはこれらの塩、又はこれらの組み合わせであるのが好ましい。過塩素酸、塩素酸、亜塩素酸、次亜塩素酸、臭素酸、ホウ酸の塩としては、これらの金属塩、又はアンモニウム塩などを用いることができる。 It is preferable that the oxo acid or a salt thereof is perchloric acid, chloric acid, chlorous acid, hypochloric acid, bromic acid, boric acid, or a salt thereof, or a combination thereof. As the salt of perchloric acid, chloric acid, chloric acid, hypochloric acid, bromic acid, boric acid, these metal salts, ammonium salts and the like can be used.
本発明の実施形態に係る化成処理用金属着色液におけるオキソ酸若しくはその塩の合計含有量は、０．５～１００ｇ／Ｌとすることができる。基本的には、オキソ酸若しくはその塩の合計含有量が少ないほど、金属表面を薄い黄色～濃い黄色系の色調に着色することができる。また、オキソ酸若しくはその塩の合計含有量が多いほど、金属表面を薄い茶色～濃い茶色系の色調に着色することができる。オキソ酸若しくはその塩の合計含有量は、１～５０ｇ／Ｌであることがより好ましく、１０～３０ｇ／Ｌであることがより好ましい。 The total content of oxoacid or a salt thereof in the metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention can be 0.5 to 100 g / L. Basically, the smaller the total content of oxoacid or a salt thereof, the lighter yellow to deeper yellowish the color of the metal surface can be. Further, the larger the total content of oxoacid or a salt thereof, the more the metal surface can be colored in a light brown to dark brown color tone. The total content of the oxoacid or a salt thereof is more preferably 1 to 50 g / L, and more preferably 10 to 30 g / L.
（水性媒体）
本発明の実施形態に係る化成処理用金属着色液は、前述の各種成分に、水性媒体を混合したものであってもよい。水性媒体は、水を主成分とする媒体を示す。水性媒体としては、例えば、水を主成分とし、水と混和可能なアルコール等の有機溶媒を含む媒体が挙げられる。水性媒体は、本発明の実施形態に係る化成処理用金属着色液の調製の際、化成処理用金属着色液の保存の際、又は金属表面を着色した後において、当該金属の着色表面の何らかの特性向上のために有利に作用する各種の成分、又は本発明の効果を実質的に阻害しない各種成分を、必要に応じて含むことができる。例えばｐＨ調整剤、保存安定剤等は、そのような成分の具体例である。
(Aqueous medium)
The metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention may be a mixture of the above-mentioned various components and an aqueous medium. The aqueous medium indicates a medium containing water as a main component. Examples of the aqueous medium include a medium containing water as a main component and containing an organic solvent such as alcohol which is miscible with water. The aqueous medium has some characteristics of the colored surface of the metal during the preparation of the metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention, during the storage of the metal coloring liquid for chemical conversion treatment, or after coloring the metal surface. Various components that act advantageously for improvement or various components that do not substantially impair the effects of the present invention can be contained, if necessary. For example, pH regulators, storage stabilizers and the like are specific examples of such components.
〔金属着色処理方法〕
次に、本発明の実施形態に係る金属着色処理方法について詳述する。まず、本発明の実施形態に係る化成処理用金属着色液が入った浴槽を準備する。次に、浴槽中の化成処理用金属着色液の温度を制御しながら、処理対象の金属を化成処理用金属着色液に浸漬する。所定時間経過後、浴槽から処理対象の金属を引き上げることで、金属表面が黄色～茶色系の色調に着色された金属を得る。このように、本発明の実施形態に係る金属着色処理方法によれば、処理対象の金属を化成処理用金属着色液に浸漬するだけで、黄色～茶色系の色調に着色することができる。このため、金属表面を黄色～茶色系の色調に着色する際に、当該金属の表面に酸化膜を形成しておく必要もなく、電解によって着色する必要もなくなり、処理効率が良好となる。
[Metal coloring treatment method]
Next, the metal coloring treatment method according to the embodiment of the present invention will be described in detail. First, a bathtub containing a metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention is prepared. Next, the metal to be treated is immersed in the metal coloring liquid for chemical conversion treatment while controlling the temperature of the metal coloring liquid for chemical conversion treatment in the bathtub. After a lapse of a predetermined time, the metal to be treated is pulled up from the bathtub to obtain a metal whose metal surface is colored in a yellow to brownish color. As described above, according to the metal coloring treatment method according to the embodiment of the present invention, the metal to be treated can be colored in a yellow to brown color tone only by immersing it in the metal coloring liquid for chemical conversion treatment. Therefore, when the metal surface is colored in a yellow to brownish color tone, it is not necessary to form an oxide film on the surface of the metal, and it is not necessary to color the metal surface by electrolysis, so that the treatment efficiency is improved.
また、本発明の実施形態に係る金属着色処理方法において、処理対象の金属を化成処理用金属着色液に浸漬する以外に、例えば、化成処理用金属着色液を用いた吹き付け工程によって、処理対象の金属の表面に化成処理用金属着色液を接触させて、処理対象の金属の表面を着色してもよい。 Further, in the metal coloring treatment method according to the embodiment of the present invention, in addition to immersing the metal to be treated in the metal coloring liquid for chemical conversion treatment, for example, the treatment target is subjected to a spraying step using the metal coloring liquid for chemical conversion treatment. The surface of the metal to be treated may be colored by contacting the surface of the metal with a metal coloring liquid for chemical conversion treatment.
化成処理用金属着色液による処理温度は、１０～８０℃の範囲が好ましく、１０～６０℃の範囲がより好ましく、３０～６０℃の範囲が更により好ましい。処理温度が１０℃以上であると表面処理の反応速度が増し、８０℃以下であると蒸発による化成処理用金属着色液の液面の低下を抑制することができる。 The treatment temperature with the metal colorant for chemical conversion treatment is preferably in the range of 10 to 80 ° C, more preferably in the range of 10 to 60 ° C, and even more preferably in the range of 30 to 60 ° C. When the treatment temperature is 10 ° C. or higher, the reaction rate of the surface treatment is increased, and when the treatment temperature is 80 ° C. or lower, the decrease in the liquid level of the metal coloring liquid for chemical conversion treatment due to evaporation can be suppressed.
化成処理用金属着色液による処理時間は、３０秒～２０分間の範囲が好ましく、１分～２０分間の範囲がより好ましく、１分～１０分間の範囲が更により好ましい。基本的には、処理時間が短いほど、金属表面を薄い黄色～濃い黄色系の色調に着色することができる。また、処理時間が長いほど、金属表面を薄い茶色～濃い茶色系の色調に着色することができる。 The treatment time with the metal colorant for chemical conversion treatment is preferably in the range of 30 seconds to 20 minutes, more preferably in the range of 1 minute to 20 minutes, and even more preferably in the range of 1 minute to 10 minutes. Basically, the shorter the treatment time, the lighter yellow to deep yellowish the color of the metal surface can be. Further, the longer the treatment time, the more the metal surface can be colored in a light brown to dark brown color tone.
金属表面処理を行う際、あらかじめ処理対象の金属の脱脂、活性化、表面調整を行うことで、処理対象の金属の外観、耐食性及び化成処理用金属着色液との反応性を向上させることが可能である。 When performing metal surface treatment, it is possible to improve the appearance, corrosion resistance, and reactivity with the metal colorant for chemical conversion treatment by degreasing, activating, and surface-adjusting the metal to be treated in advance. Is.
金属表面処理後に、ケイ素、樹脂及びワックスからなる群のうちの１種以上を含有するコーティング剤にて後処理を行っても良い。所望の金属表面の色調に影響を与えない範囲において、これらコーティング剤に特に限定はなく、アクリル樹脂、オレフィン樹脂、アルキド樹脂、尿素樹脂、エポキシ樹脂、メラミン樹脂、フッ素樹脂、ポリエチレン、ポリ塩化ビニル、ポリスチレン、ポリプロピレン、メタクリル樹脂、フェノール樹脂、ポリエステル樹脂、ポリウレタン、ポリアミド、ポリカーボネート等の樹脂類やケイ酸塩、コロイダルシリカ等を成分とするコーティング剤を用いても良い。これらの樹脂濃度は、０．０１～８００ｇ／Ｌが好ましいが、適切な濃度は樹脂の種類により異なる。コーティング剤としては、具体的には、コスマーコート（商品名、関西ペイント（株））、ハイシール２７２（商品名、日本表面化学（株））、ストロンＪＳコート（商品名、日本表面化学（株））、トライナーＴＲ－１７０（商品名、日本表面化学（株））、フィニガード（商品名、Coventya社）等が挙げられる。アクリル樹脂としては、具体的には、ヒロタイト（商品名、日立化成（株））、アロセット（商品名、（株）日本触媒）等があり、オレフィン樹脂については、フローセン（商品名、住友精化（株））、ＰＥＳ（商品名、日本ユニカー（株））、ケミパール（商品名、三井化学（株））、サンファイン（商品名、旭化成（株））等が挙げられる。 After the metal surface treatment, the post-treatment may be performed with a coating agent containing at least one of the group consisting of silicon, resin and wax. The coating agents are not particularly limited as long as they do not affect the color tone of the desired metal surface, and acrylic resin, olefin resin, alkyd resin, urea resin, epoxy resin, melamine resin, fluororesin, polyethylene, polyvinyl chloride, etc. A coating agent containing resins such as polystyrene, polypropylene, methacrylic resin, phenol resin, polyester resin, polyurethane, polyamide, and polycarbonate, silicate, colloidal silica, and the like may be used. The concentration of these resins is preferably 0.01 to 800 g / L, but the appropriate concentration varies depending on the type of resin. Specifically, as the coating agent, Cosmer Coat (trade name, Kansai Paint Co., Ltd.), High Seal 272 (trade name, Nippon Surface Chemical Co., Ltd.), Stron JS Coat (trade name, Nippon Surface Chemical Co., Ltd.) ), Triner TR-170 (trade name, Nippon Surface Chemical Co., Ltd.), Finigard (trade name, Coventya Co., Ltd.) and the like. Specific examples of acrylic resins include Hirotite (trade name, Hitachi Kasei Co., Ltd.), Arosett (trade name, Nippon Shokubai Co., Ltd.), and Frosen (trade name, Sumitomo Seika Co., Ltd.) for olefin resins. (Co., Ltd.), PES (trade name, Nippon Unicar Co., Ltd.), Chemipearl (trade name, Mitsui Kagaku Co., Ltd.), Sunfine (trade name, Asahi Kasei Co., Ltd.) and the like.
本発明の実施形態に係る化成処理用金属着色液は、金属表面を、所望の色に着色させる、所望の美観を付与する、又は識別性を付与する等の目的で使用することができる。このような処理対象の金属の形態としては、あらゆるものを用いることができ、特に限定されないが、例えば、装飾品、ボタンやファスナー等のファスニング部材、車載用部品等を用いることができる。また、当該処理対象の金属の形状についても限定されず、あらゆる形状のものを用いることができる。 The metal coloring liquid for chemical conversion treatment according to the embodiment of the present invention can be used for the purpose of coloring the metal surface to a desired color, imparting a desired aesthetic appearance, imparting distinctiveness, and the like. Any form of the metal to be processed can be used, and the form thereof is not particularly limited, and for example, ornaments, fastening members such as buttons and fasteners, in-vehicle parts, and the like can be used. Further, the shape of the metal to be treated is not limited, and any shape can be used.
以下、本発明の実施例を示すが、これらは本発明をより良く理解するために提供するものであり、本発明が限定されることを意図するものではない。 Hereinafter, examples of the present invention will be shown, but these are provided for a better understanding of the present invention, and are not intended to limit the present invention.
〔試験例１：アルミニウム、アルミニウム合金の着色試験〕
（実施例１～８３、９０、９１）
試験片（処理対象の金属片）として、ＪＩＳ Ａ５０５２（アルミニウム－マグネシウム合金）、Ａ２０１７（アルミニウム－銅合金）、ＡＤＣ１２（アルミダイキャスト）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表１～６、８に示す液組成の化成処理用金属着色液を入れた浴槽を準備した。化成処理用金属着色液の水性媒体は純水を使用した。
次に、浴槽中の化成処理用金属着色液を表１～６、８に示す温度に制御した状態で、試験片を浸漬した。表１～６、８に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 1: Coloring test of aluminum and aluminum alloy]
(Examples 1 to 83, 90, 91)
JIS A5052 (aluminum-magnesium alloy), A2017 (aluminum-copper alloy), and ADC12 (aluminum die-cast) are prepared as test pieces (metal pieces to be treated), and the surface of the test piece is degreased and washed with water in order. went.
Next, a bathtub containing a metal coloring liquid for chemical conversion treatment having the liquid compositions shown in Tables 1 to 6 and 8 was prepared. Pure water was used as the aqueous medium for the metal colorant for chemical conversion treatment.
Next, the test piece was immersed in a state where the metal coloring liquid for chemical conversion treatment in the bathtub was controlled to the temperatures shown in Tables 1 to 6 and 8. After soaking for the time shown in Tables 1 to 6 and 8, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
なお、実施例９０及び９１については、浸漬により皮膜（着色皮膜）を形成した後の試験片を水洗し、コーティング処理を行い、乾燥した。実施例９０のコーティング処理にはストロンＪＳコート（日本表面化学（株）製コーティング剤）、実施例９１のコーティング処理にはＴＲ－１７０（日本表面化学（株）製コーティング剤）を使用した。 For Examples 90 and 91, the test piece after forming the film (colored film) by immersion was washed with water, coated, and dried. Stron JS coat (coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was used for the coating treatment of Example 90, and TR-170 (coating agent manufactured by Nippon Surface Chemical Co., Ltd.) was used for the coating treatment of Example 91.
〔試験例２：銅、銅合金の着色試験〕
（実施例８４～８５）
試験片（処理対象の金属片）として、ＪＩＳ Ｃ２６００Ｐ（真鍮）、Ｃ１１００Ｐ（純銅）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表７に示す液組成の化成処理用金属着色液を入れた浴槽を準備した。化成処理用金属着色液の水性媒体は純水を使用した。
次に、浴槽中の化成処理用金属着色液を表７に示す温度に制御した状態で、試験片を浸漬した。表７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 2: Coloring test of copper and copper alloy]
(Examples 84 to 85)
JIS C2600P (brass) and C1100P (pure copper) were prepared as test pieces (metal pieces to be treated), and the surface of the test pieces was degreased and washed with water in this order.
Next, a bathtub containing a metal coloring liquid for chemical conversion treatment having the liquid composition shown in Table 7 was prepared. Pure water was used as the aqueous medium for the metal colorant for chemical conversion treatment.
Next, the test piece was immersed in a state where the metal coloring liquid for chemical conversion treatment in the bathtub was controlled to the temperature shown in Table 7. After soaking for the time shown in Table 7, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例３：亜鉛、亜鉛合金の着色試験〕
（実施例８６～８７）
試験片（処理対象の金属片）として、ＪＩＳ ＺＤＣ２（亜鉛ダイキャスト）及び亜鉛めっき材を準備し、当該試験片の表面に、脱脂、水洗を順に行った。当該亜鉛めっき材は、ＪＩＳで規定されるＪＩＳ ＳＰＣＣ（圧延鋼板）を基材として、膜厚８μｍのジンケート亜鉛メッキを施したものである。また、当該ジンケート亜鉛メッキの光沢剤として、日本表面化学（株）製９０００ＡＢＳを使用した。
次に、表７に示す液組成の化成処理用金属着色液を入れた浴槽を準備した。化成処理用金属着色液の水性媒体は純水を使用した。
次に、浴槽中の化成処理用金属着色液を表７に示す温度に制御した状態で、試験片を浸漬した。表７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 3: Coloring test of zinc and zinc alloy]
(Examples 86 to 87)
JIS ZDC2 (zinc die-cast) and a zinc-plated material were prepared as test pieces (metal pieces to be treated), and the surface of the test pieces was degreased and washed with water in this order. The zinc-plated material is a zinc-plated material having a thickness of 8 μm, using JIS SPCC (rolled steel sheet) specified by JIS as a base material. Further, as the brightener for the zincate zinc plating, 9000 ABS manufactured by Nippon Surface Chemical Co., Ltd. was used.
Next, a bathtub containing a metal coloring liquid for chemical conversion treatment having the liquid composition shown in Table 7 was prepared. Pure water was used as the aqueous medium for the metal colorant for chemical conversion treatment.
Next, the test piece was immersed in a state where the metal coloring liquid for chemical conversion treatment in the bathtub was controlled to the temperature shown in Table 7. After soaking for the time shown in Table 7, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例４：鉄、鉄合金の着色試験〕
（実施例８８）
試験片（処理対象の金属片）として、ＪＩＳ ＳＰＣＣ（圧延鋼板）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表７に示す液組成の化成処理用金属着色液を入れた浴槽を準備した。化成処理用金属着色液の水性媒体は純水を使用した。
次に、浴槽中の化成処理用金属着色液を表７に示す温度に制御した状態で、試験片を浸漬した。表７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 4: Coloring test of iron and iron alloy]
(Example 88)
JIS SPCC (rolled steel sheet) was prepared as a test piece (metal piece to be treated), and the surface of the test piece was degreased and washed with water in this order.
Next, a bathtub containing a metal coloring liquid for chemical conversion treatment having the liquid composition shown in Table 7 was prepared. Pure water was used as the aqueous medium for the metal colorant for chemical conversion treatment.
Next, the test piece was immersed in a state where the metal coloring liquid for chemical conversion treatment in the bathtub was controlled to the temperature shown in Table 7. After soaking for the time shown in Table 7, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例５：マグネシウム、マグネシウム合金の着色試験〕
（実施例８９）
試験片（処理対象の金属片）として、ＪＩＳ ＡＺ３１（マグネシウム－亜鉛合金）を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表７に示す液組成の化成処理用金属着色液を入れた浴槽を準備した。化成処理用金属着色液の水性媒体は純水を使用した。
次に、浴槽中の化成処理用金属着色液を表７に示す温度に制御した状態で、試験片を浸漬した。表７に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 5: Coloring test of magnesium and magnesium alloy]
(Example 89)
JIS AZ31 (magnesium-zinc alloy) was prepared as a test piece (metal piece to be treated), and the surface of the test piece was degreased and washed with water in this order.
Next, a bathtub containing a metal coloring liquid for chemical conversion treatment having the liquid composition shown in Table 7 was prepared. Pure water was used as the aqueous medium for the metal colorant for chemical conversion treatment.
Next, the test piece was immersed in a state where the metal coloring liquid for chemical conversion treatment in the bathtub was controlled to the temperature shown in Table 7. After soaking for the time shown in Table 7, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔試験例６〕
（比較例１～４）
試験片（処理対象の金属片）として、表９に示す金属を準備し、当該試験片の表面に、脱脂、水洗を順に行った。
次に、表９に示す液組成の化成処理用金属着色液を入れた浴槽を準備した。化成処理用金属着色液の水性媒体は純水を使用した。
次に、浴槽中の化成処理用金属着色液を表９に示す温度に制御した状態で、試験片を浸漬した。表９に示す時間だけ浸漬させた後、試験片を取り出した。次に、試験片の表面を水洗し、続いて乾燥した。
[Test Example 6]
(Comparative Examples 1 to 4)
As a test piece (metal piece to be treated), the metal shown in Table 9 was prepared, and the surface of the test piece was degreased and washed with water in this order.
Next, a bathtub containing a metal coloring liquid for chemical conversion treatment having the liquid composition shown in Table 9 was prepared. Pure water was used as the aqueous medium for the metal colorant for chemical conversion treatment.
Next, the test piece was immersed in a state where the metal coloring liquid for chemical conversion treatment in the bathtub was controlled to the temperature shown in Table 9. After soaking for the time shown in Table 9, the test piece was taken out. Next, the surface of the test piece was washed with water and then dried.
〔各種評価〕
実施例１～９１及び比較例１～４で作製した試験片について、色調評価及び密着性評価を以下の通り行った。
[Various evaluations]
The test pieces prepared in Examples 1 to 91 and Comparative Examples 1 to 4 were evaluated for color tone and adhesion as follows.
（色調評価）
試験片の表面の色調は、目視により評価した。評価基準を以下に示す。
Ａ：均一で美観に優れた処理外観を有する黄色
Ｂ：均一で美観に優れた処理外観を有するＡよりも濃い黄色
Ｃ：均一で美観に優れた処理外観を有するＡよりも薄い黄色
Ｄ：均一で美観に優れた処理外観を有する茶色
Ｅ：均一で美観に優れた処理外観を有するＤよりも濃い茶色
Ｆ：均一で美観に優れた処理外観を有するＤよりも薄い茶色
Ｇ：着色なし
(Color tone evaluation)
The color tone of the surface of the test piece was visually evaluated. The evaluation criteria are shown below.
A: Yellow with uniform and aesthetically pleasing treated appearance B: Darker yellow than A with uniform and aesthetically pleasing treated appearance C: Lighter yellow than A with uniform and aesthetically pleasing treated appearance D: Uniform Brown with a uniform and aesthetically pleasing treated appearance E: Darker brown than D with a uniform and aesthetically pleasing treated appearance F: Lighter brown than D with a uniform and aesthetically pleasing treated appearance G: No coloring
（密着性評価）
試験片の表面に、カッターで１０×１０マス（合計１００マス）の切り込みを入れ、セロテープ（登録商標）を貼って剥がした際に、着色皮膜が剥がれなかったマス目の数をカウントした。１マス分のサイズは、縦×横＝１ｍｍ×１ｍｍであった。
各表には、（着色皮膜が剥がれなかったマス目の数）／１００で示しており、着色皮膜が剥がれなかったマス目の数が大きいほど着色皮膜の密着性が高いことを示している。
(Adhesion evaluation)
A notch of 10 × 10 squares (100 squares in total) was made on the surface of the test piece, and the number of squares in which the colored film was not peeled off when the cellophane tape (registered trademark) was attached and peeled off was counted. The size of one square was vertical × horizontal = 1 mm × 1 mm.
In each table, it is shown by (the number of squares in which the colored film did not peel off) / 100, and it is shown that the larger the number of squares in which the colored film did not peel off, the higher the adhesion of the colored film.
実施例１～９１及び比較例１～４について、試験条件及び評価結果を表１～９に示す。 The test conditions and evaluation results for Examples 1 to 91 and Comparative Examples 1 to 4 are shown in Tables 1 to 9.
以上の結果から、実施例１～９１のように、過マンガン酸若しくはその塩と、無機酸及びその塩のいずれか一方又は両方と、縮合リン酸塩とを含む化成処理用金属着色液によれば、良好な処理効率で金属表面を黄色～茶色系の色調に着色することができることが確認された。
一方、比較例１～４のように、化成処理用金属着色液が過マンガン酸若しくはその塩と、無機酸及びその塩のいずれか一方又は両方と、縮合リン酸塩とを含まないと、金属表面を黄色～茶色系の色調に着色することができないことが確認された。
From the above results, as in Examples 1 to 91, a metal coloring liquid for chemical conversion treatment containing permanganic acid or a salt thereof, one or both of an inorganic acid and a salt thereof, and a condensed phosphate is used. For example, it was confirmed that the metal surface can be colored in a yellow to brownish color with good treatment efficiency.
On the other hand, as in Comparative Examples 1 to 4, if the metal coloring liquid for chemical conversion treatment does not contain permanganic acid or a salt thereof, one or both of an inorganic acid and a salt thereof, and a condensed phosphate, the metal It was confirmed that the surface could not be colored in a yellow to brownish tone.
Claims (13)
無機酸及びその塩のいずれか一方又は両方と、
縮合リン酸塩と、
を含む化成処理用金属着色液。 With permanganate or its salt,
With one or both of the inorganic acid and its salt,
Condensed phosphate and
Metal colorant for chemical conversion treatment including.
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| JPS54107438A (en) * | 1978-02-09 | 1979-08-23 | Furukawa Electric Co Ltd:The | Coloring of aluminum |
| US4252932A (en) | 1979-12-03 | 1981-02-24 | Dow Corning Corporation | Oxygen-curable mercaptoorganosiloxane compositions catalyzed by metal carbonyl compounds and method of forming higher molecular weight products therefrom |
| JPS60110895A (en) | 1983-11-21 | 1985-06-17 | Nippon Alum Mfg Co Ltd:The | Electrolytic coloring method of aluminum and aluminum alloy |
| JP2001123274A (en) * | 1999-10-25 | 2001-05-08 | Mitsui Mining & Smelting Co Ltd | High corrosion resistance surface treated magnesium alloy product and producing method therefor |
| JP3903381B2 (en) * | 2002-11-20 | 2007-04-11 | 三井金属鉱業株式会社 | How to paint aluminum alloy |
| JP3765814B2 (en) * | 2003-09-26 | 2006-04-12 | 株式会社シミズ | Ground treatment solution for metal coating and coating method |
| KR100855358B1 (en) * | 2006-10-20 | 2008-09-04 | (주)보광사 | Chemical Coating Solutions for Magnesium Alloys, Environmental-affinitive Surface Treating Methods Using the Same, and Magnesium Alloy Substrates thereby |
| CN104894552A (en) * | 2015-06-19 | 2015-09-09 | 海安县申菱电器制造有限公司 | Method for forming golden yellow film on surface of aluminum alloy |
-
2020
- 2020-07-06 JP JP2020116562A patent/JP2022014297A/en active Pending
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2021
- 2021-06-17 DE DE102021003120.2A patent/DE102021003120A1/en active Pending
- 2021-06-29 US US17/362,705 patent/US20220018027A1/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7489661B2 (en) | 2020-07-06 | 2024-05-24 | Ykk株式会社 | Aluminum alloy fastening member, fastener chain, and method for manufacturing an aluminum alloy fastening member |
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| Publication number | Publication date |
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| FR3112150B1 (en) | 2023-10-20 |
| US20220018027A1 (en) | 2022-01-20 |
| DE102021003120A1 (en) | 2022-01-13 |
| FR3112150A1 (en) | 2022-01-07 |
| CN113897606A (en) | 2022-01-07 |
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