JP2014205871A - Method of treating surface of copper-based metal to color blue - Google Patents
Method of treating surface of copper-based metal to color blue Download PDFInfo
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- JP2014205871A JP2014205871A JP2013082759A JP2013082759A JP2014205871A JP 2014205871 A JP2014205871 A JP 2014205871A JP 2013082759 A JP2013082759 A JP 2013082759A JP 2013082759 A JP2013082759 A JP 2013082759A JP 2014205871 A JP2014205871 A JP 2014205871A
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- based metal
- chlorite
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 98
- 239000010949 copper Substances 0.000 title claims abstract description 98
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 92
- 239000002184 metal Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000011282 treatment Methods 0.000 claims abstract description 92
- 239000000126 substance Substances 0.000 claims abstract description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910001919 chlorite Inorganic materials 0.000 claims abstract description 21
- 229910052619 chlorite group Inorganic materials 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 238000004040 coloring Methods 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 17
- 235000011007 phosphoric acid Nutrition 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical class [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 7
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 6
- 150000002334 glycols Chemical class 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 5
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 4
- 238000003672 processing method Methods 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical group [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 229960002218 sodium chlorite Drugs 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 10
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 238000004043 dyeing Methods 0.000 description 31
- 238000007747 plating Methods 0.000 description 29
- 238000012545 processing Methods 0.000 description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005238 degreasing Methods 0.000 description 13
- 239000003973 paint Substances 0.000 description 13
- 229910001369 Brass Inorganic materials 0.000 description 12
- 239000010951 brass Substances 0.000 description 12
- 238000007654 immersion Methods 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 8
- 239000003086 colorant Substances 0.000 description 7
- 238000002845 discoloration Methods 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- -1 phosphorus oxo acid Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 235000011180 diphosphates Nutrition 0.000 description 2
- 238000004649 discoloration prevention Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 2
- 235000019828 potassium polyphosphate Nutrition 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- QXIKMJLSPJFYOI-UHFFFAOYSA-L calcium;dichlorite Chemical compound [Ca+2].[O-]Cl=O.[O-]Cl=O QXIKMJLSPJFYOI-UHFFFAOYSA-L 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229940077239 chlorous acid Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011369 optimal treatment Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- VISKNDGJUCDNMS-UHFFFAOYSA-M potassium;chlorite Chemical compound [K+].[O-]Cl=O VISKNDGJUCDNMS-UHFFFAOYSA-M 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000019830 sodium polyphosphate Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
Description
本発明は、ブローチ、ボタン、バックル、ファスナー、カフスボタン等の衣類に使用される服飾品、ネックレス、イアリング等の装飾品、および玩具、その他工業用品等に利用さる銅系金属の表面外観を、有機系塗料を使用せず青色の色調に着色するための処理方法に関するものである。さらに詳しく言えば、銅、銅−錫系合金、銅−亜鉛系合金を、特定の亜塩素酸塩系化成処理液中で浸漬処理することにより、表面の外観を青色の色調に着色させる処理方法、前記処理方法で銅系金属を処理する表面が青色の色調を有する銅系金属の製造方法、および前記製造方法により製造された銅系金属からなる服飾品または装飾品等に関するものである。 The present invention provides a surface appearance of a copper-based metal used in clothing such as brooches, buttons, buckles, fasteners, cufflinks, ornaments such as necklaces and earrings, and toys and other industrial products. The present invention relates to a processing method for coloring a blue color tone without using an organic paint. More specifically, a treatment method for coloring the surface appearance to a blue color tone by immersing copper, a copper-tin alloy, or a copper-zinc alloy in a specific chlorite chemical conversion treatment solution. Further, the present invention relates to a method for producing a copper-based metal having a blue color tone on the surface where the copper-based metal is treated by the treatment method, and an article of clothing or decoration made of the copper-based metal produced by the production method.
衣料品メーカーでは、衣類、袋物等の縫製の際に使用する針が衣類中に残留することによる人体への刺傷の危険性が問題視されており、これを防止するために磁気探針が実施されている。そのため、服飾品の金属としては、磁性のない非磁性の金属を使用することが必要である。従来、非磁性の金属としてはニッケルと比較してアレルゲンになりにくい物質である銅系の金属を使用することが多い。 In clothing manufacturers, the risk of stinging the human body due to the needles used to sew clothing, bags, etc. remains in the clothing, and magnetic probes are used to prevent this. Has been. Therefore, it is necessary to use a non-magnetic metal having no magnetism as a metal for clothing. Conventionally, as a nonmagnetic metal, a copper-based metal, which is a substance that is less likely to become an allergen than nickel, is often used.
これら銅系金属を、実際に服飾品または装飾品等の分野で使用するにあたっては、その表面（外観）がどのような色調であるかが重要であり、服飾品、装飾品等の製造に関わるメーカーにとって、他の製品との差別化をはかる色調の製品を提供することが関心事であり、また要求される品質ともなっている。 When these copper-based metals are actually used in the field of apparel or ornaments, it is important what color the surface (appearance) is, and it is involved in the production of apparel and ornaments. For manufacturers, it is a matter of concern and quality that is required to provide products with colors that differentiate them from other products.
そこで、銅系金属の表面を着色する従来の方法としては主に下記の(1)および(2)に大別される。
(1)有機系塗料等により表面コーティングする方法、すなわち、所望の色を発色させるために顔料または染料を適宜含有した有機系塗料により塗装（コーティング）する方法。
(2)有機系塗料を使用しない方法として、例えば、金属それ自体の色調をそのまま利用する方法、あるいは、金属表面に何らかの化成処理を施すことにより表面を特定の色に着色（発色）させる方法。
Therefore, conventional methods for coloring the surface of a copper-based metal are roughly classified into the following (1) and (2).
(1) A method of surface coating with an organic paint or the like, that is, a method of coating (coating) with an organic paint appropriately containing a pigment or a dye in order to develop a desired color.
(2) As a method not using an organic paint, for example, a method using the color tone of the metal itself as it is, or a method of coloring (coloring) the surface to a specific color by performing some chemical conversion treatment on the metal surface.
しかし、(1)による有機系塗料のコーティングによる方法では、顔料、染料の選択、組み合わせにより、任意の様々な色に着色可能である反面、着色部分が有機系皮膜であるため皮膜の傷が付きやすく、また、設備面、環境面でコスト的な負担が大きい等の問題がある。 However, in the method of coating with organic paint according to (1), it is possible to color in various colors by selecting and combining pigments and dyes, but the film is scratched because the colored part is an organic film. There is a problem that it is easy and the cost burden is large in terms of facilities and environment.
一方、(2)の有機系塗料を使用しない方法としては、まず、金属自体が本来持っている色調を利用する方法が挙げられる。例えば、銅−錫合金においては、金属中の銅および錫の含有率を変えることにより、赤黄〜銀白色〜白色（電着合金の場合）、銅赤色〜灰黄色〜銀白色〜暗灰色〜淡灰色〜蒼灰色〜銀灰色（鋳造合金の場合）等の外観色が得られることが知られている。特許文献１、特許文献２または特許文献４においては、銅−錫合金めっきとして、赤銅色、黄色（黄金色）、白色、銀白色等の色調のものが記載されている。また、特許文献３および特許文献４においては、特殊な添加剤、界面活性剤等を添加しためっき浴でめっきすることにより、黒色系の色調を有した銅−錫合金めっきが提案されている。
銅−亜鉛合金においても同様に、金属中の銅、亜鉛の含有率を変化させることにより、赤（銅色）〜黄色〜灰色等の外観が得られることが知られている。
On the other hand, as a method (2) that does not use an organic paint, first, there is a method that uses the color tone inherent to the metal itself. For example, in a copper-tin alloy, by changing the content of copper and tin in the metal, red yellow to silver white to white (in the case of an electrodeposited alloy), copper red to gray yellow to silver white to dark gray to It is known that appearance colors such as light gray to dark gray to silver gray (in the case of a cast alloy) can be obtained. In Patent Document 1, Patent Document 2 or Patent Document 4, copper-tin alloy plating having a color tone such as red copper color, yellow (golden color), white, or silver white is described. In Patent Document 3 and Patent Document 4, copper-tin alloy plating having a black color tone is proposed by plating in a plating bath to which a special additive, a surfactant or the like is added.
Similarly, in copper-zinc alloys, it is known that appearances such as red (copper color) to yellow to gray can be obtained by changing the contents of copper and zinc in the metal.
次に、金属表面に何らかの化成処理（後処理）を施すことにより着色させる方法としては、古くから銅系金属（および鉄系金属）のような金属を黒色化させる用途として、各種薬品メーカーより強アルカリの薬液（亜塩素酸塩系溶液等）等による各種黒染め処理（黒色化処理）薬液が市販されており、これにより銅、鉄系金属においては黒色の色調が得られることが広く知られている。
しかし、従来の有機系塗料を用いないこれらの方法では、本発明が狙いとする銅表面を青色の色調に着色することを提案するには至っていない。
Next, as a method of coloring by performing some chemical conversion treatment (post-treatment) on the metal surface, it has been stronger than various chemical manufacturers as an application to blacken metals such as copper-based metals (and iron-based metals) for a long time. Various black dyeing (blackening) chemicals are commercially available, such as alkaline chemicals (chlorite solutions, etc.), and it is widely known that black color tone can be obtained for copper and iron-based metals. ing.
However, these conventional methods that do not use organic paints have not yet proposed that the copper surface targeted by the present invention is colored in a blue tone.
以上のように、表面の外観が青色系の色調を有した銅系金属は、青色系の顔料、または染料が含有する有機系塗料等によるコーティングが現在その主流であると考えられ、有機系塗料を使用しないで銅系金属の表面を青色に着色する処理方法は実用化されていない。そのため、有機系塗料を使用せず銅系金属の表面を青色系の色調に着色するための処理方法の確立が望まれていた。 As described above, it is considered that the coating of the blue-based copper-based metal having a blue color tone with an organic paint containing a blue pigment or dye is currently the mainstream. A treatment method for coloring the surface of a copper-based metal in blue without using a metal has not been put into practical use. Therefore, establishment of the processing method for coloring the surface of a copper-type metal in a blue color tone without using an organic coating material was desired.
従って、本発明の課題は、有機系塗料によるコーティングによらず、銅系金属の表面を青色に着色するための処理方法およびこの処理方法により製造される銅系金属からなる服飾品または装飾品を提供することにある。 Accordingly, an object of the present invention is to provide a treatment method for coloring the surface of a copper-based metal in blue, regardless of coating with an organic paint, and a clothing or ornament made of a copper-based metal produced by this treatment method. It is to provide.
本発明者らは、銅系金属表面を、顔料または染料を含んだ有機系塗料等をコーティングした有機系皮膜に頼らずに青色に着色するために、銅系金属への無機系処理液による化成処理に関して鋭意検討を行った結果、銅系金属表面を特定の亜塩素酸塩系化成処理液で処理することが有効であることを見出して本発明を完成するに至った。 In order to color the copper-based metal surface in blue without relying on an organic film coated with an organic paint containing a pigment or a dye, the present inventors have formed a copper-based metal with an inorganic treatment liquid. As a result of intensive studies on the treatment, the present inventors have found that it is effective to treat the copper-based metal surface with a specific chlorite-based chemical conversion treatment liquid, and have completed the present invention.
本発明は、下記［１］〜［８］の銅系金属表面の青色着色処理方法、［９］の表面が青色の色調を有する銅系金属の製造方法、および［１０］の表面が青色の色調を有する銅系金属からなる服飾品および装飾品に関するものである。
［１］亜塩素酸塩類を０．５〜２５０ｇ／Ｌ、アルカリ金属の水酸化物を１〜６２５ｇ／Ｌ含有する亜塩素酸塩系化成処理液に銅系金属を浸漬処理することを特徴とする銅系金属表面の青色着色処理方法。
［２］亜塩素酸塩系化成処理液が、さらにリン酸類およびグリコール類から選択される少なくとも１種を含有する前項１に記載の銅系金属表面の青色着色処理方法。
［３］亜塩素酸塩系化成処理液のリン酸類含有量が０．１〜５０ｇ／Ｌ、グリコール類含有量が０．０１〜５ｇ／Ｌである前項２に記載の銅系金属表面の青色着色処理方法。
［４］亜塩素酸塩類が亜塩素酸ナトリウムであり、アルカリ金属の水酸化物が水酸化ナトリウムである前項１〜３のいずれかに記載の銅系金属表面の青色着色処理方法。
［５］リン酸類がポリリン酸であり、グリコール類がエチレングリコールである前項２〜４のいずれかに記載の銅系金属表面の青色着色処理方法。
［６］銅系金属が、銅、銅−錫系合金、または銅−亜鉛系合金である前項１〜５のいずれかに記載の銅系金属表面の青色着色処理方法。
［７］青色の色調が、マンセル表色系で表した場合の色相（Ｈ）がＧＹ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、青紫（ＰＢ）、紫（Ｐ）で分類される色相である前項１〜６のいずれかに記載の銅系金属表面の青色着色処理方法。
［８］青色の色調のマンセル表色系で表した場合の明度（Ｖ）が２以上８．５以下であり、彩度（Ｃ）が２以上である前項７に記載の銅系金属表面の青色着色処理方法。
［９］前項１〜８のいずれかに記載の青色着色処理方法により銅系金属を処理することを特徴とする表面が青色の色調を有する銅系金属の製造方法。
［１０］前項９に記載の方法により製造された表面が青色の色調を有する銅系金属からなる服飾品または装飾品。
The present invention includes the following [1] to [8]: a method for blue-coloring a copper-based metal surface; [9] a method for producing a copper-based metal having a blue color on the surface; and [10] a surface having a blue surface. The present invention relates to clothing and ornaments made of copper-based metal having a color tone.
[1] It is characterized by immersing a copper-based metal in a chlorite-based chemical conversion treatment solution containing 0.5 to 250 g / L of chlorite and 1 to 625 g / L of an alkali metal hydroxide. Blue color treatment method for copper-based metal surface.
[2] The blue coloring treatment method for a copper-based metal surface according to item 1 above, wherein the chlorite-based chemical conversion treatment liquid further contains at least one selected from phosphoric acids and glycols.
[3] The blue color of the surface of the copper-based metal according to item 2 above, wherein the chlorite-based chemical conversion treatment solution has a phosphoric acid content of 0.1 to 50 g / L and a glycol content of 0.01 to 5 g / L. Coloring method.
[4] The blue coloring treatment method for a copper-based metal surface according to any one of items 1 to 3, wherein the chlorite is sodium chlorite and the alkali metal hydroxide is sodium hydroxide.
[5] The blue coloring treatment method for a copper-based metal surface according to any one of items 2 to 4, wherein the phosphoric acid is polyphosphoric acid and the glycol is ethylene glycol.
[6] The blue coloring treatment method for a copper-based metal surface according to any one of items 1 to 5, wherein the copper-based metal is copper, a copper-tin-based alloy, or a copper-zinc-based alloy.
[7] When the hue of blue is expressed in the Munsell color system, the hue (H) is GY (yellowish green), G (green), BG (blue green), B (blue), blue purple (PB), purple The blue coloring treatment method for a copper-based metal surface according to any one of the preceding items 1 to 6, which is a hue classified by (P).
[8] The brightness of the copper-based metal surface according to item 7 above, wherein the brightness (V) is 2 or more and 8.5 or less and the chroma (C) is 2 or more when expressed in the Munsell color system of blue color tone. Blue coloring treatment method.
[9] A method for producing a copper-based metal having a blue color tone, wherein the copper-based metal is treated by the blue coloring treatment method according to any one of items 1 to 8 above.
[10] An article of clothing or decoration made of a copper-based metal having a blue color on the surface produced by the method described in item 9 above.
従来、銅系金属では、有機系塗料を使用してのみしか青色系の色調を得られなかったが、本発明により、有機系塗料（顔料および／または染料含む）に頼ることなく、青色の色調を有した銅系金属製品を得ることが可能となり、かつ塗装工程のない設備（生産ライン）に簡単な設備・工程を付加するのみで、簡単かつ低コストで表面が青色の色調を有する銅系金属を製造することができる。 Conventionally, with a copper-based metal, a blue color tone can be obtained only by using an organic paint, but according to the present invention, a blue color tone can be obtained without relying on an organic paint (including pigments and / or dyes). It is possible to obtain a copper-based metal product having a surface, and it is simple and low-cost with a blue-colored surface, simply by adding simple equipment and processes to equipment (production line) that does not have a painting process. Metal can be produced.
以下、本発明を詳細に説明する。
本発明は、銅系金属を、亜塩素酸塩類を０．５ｇ／Ｌ〜２５０ｇ／Ｌ、アルカリ金属の水酸化物を１ｇ／Ｌ〜６２５ｇ／Ｌ含有する水溶液で浸漬処理することを特徴とする。
亜塩素酸塩類が０．５ｇ／Ｌ未満でも、アルカリ金属の水酸化物が１ｇ／Ｌ未満でも本発明の効果が得られない。
Hereinafter, the present invention will be described in detail.
The present invention is characterized by immersing a copper-based metal in an aqueous solution containing 0.5 g / L to 250 g / L of chlorite and 1 g / L to 625 g / L of an alkali metal hydroxide. .
Even if the chlorite is less than 0.5 g / L or the alkali metal hydroxide is less than 1 g / L, the effect of the present invention cannot be obtained.
また、亜塩素酸塩類が２５０ｇ／Ｌ超、またはアルカリ金属の水酸化物が６２５ｇ／Ｌ超では、それ以上の効果が得られないか、または、処理液の酸化力が強くなりすぎるため、工業的に生産可能な処理条件が得られなくなる。さらには、生産時の薬液の持ち出しによる薬液の損失が大きくなるという問題もあり、本発明には適さない。
亜塩素酸塩類含有量は３ｇ／Ｌ〜１５０ｇ／Ｌ、アルカリ金属の水酸化物含有量は７．５ｇ／Ｌ〜３７５ｇ／Ｌが好ましく、さらに好ましくは、亜塩素酸塩類含有量は１４ｇ／Ｌ〜１１０ｇ／Ｌ、アルカリ金属の水酸化物含有量は３５ｇ／Ｌ〜２７５ｇ／Ｌである。
このように、銅系金属表面を本発明による処理液で浸漬処理することにより、青色の色調を有した外観の銅系金属が初めて得られる。
In addition, if the chlorite exceeds 250 g / L or the alkali metal hydroxide exceeds 625 g / L, no further effect can be obtained, or the oxidizing power of the treatment liquid becomes too strong. The processing conditions that can be produced in general cannot be obtained. Furthermore, there is a problem that the loss of the chemical solution due to the carry-out of the chemical solution during production becomes large, and is not suitable for the present invention.
The chlorite content is preferably 3 g / L to 150 g / L, the alkali metal hydroxide content is preferably 7.5 g / L to 375 g / L, and more preferably the chlorite content is 14 g / L. ˜110 g / L, the alkali metal hydroxide content is 35 g / L to 275 g / L.
Thus, by immersing the copper-based metal surface with the treatment liquid according to the present invention, a copper-based metal having an appearance with a blue color tone can be obtained for the first time.
本発明において使用する亜塩素酸塩類とは、亜塩素酸とアルカリ金属および／またはアルカリ土類金属の塩であり、例えば、亜塩素酸ナトリウム、亜塩素酸カリウム、亜塩素酸カルシウム等が挙げられ、中でも亜塩素酸ナトリウムが最も好ましい。また、アルカリ金属の水酸化物としては、例えば水酸化ナトリウム、水酸化カリウム等が挙げられ、中でも水酸化ナトリウムが最も好ましい。 The chlorite used in the present invention is a salt of chlorous acid and alkali metal and / or alkaline earth metal, and examples thereof include sodium chlorite, potassium chlorite, calcium chlorite and the like. Of these, sodium chlorite is most preferable. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide, and sodium hydroxide is most preferable.
さらに、本発明では、化成処理液にリン酸類またはグリコール類のいずれかを添加することが、表面の平滑性が向上するため好ましく、リン酸類、グリコール類を併用して添加することがより好ましい。 Furthermore, in the present invention, it is preferable to add either phosphoric acids or glycols to the chemical conversion treatment liquid because surface smoothness is improved, and it is more preferable to add phosphoric acids and glycols in combination.
ここでいう、リン酸類とは、リンのオキソ酸（亜リン酸、次亜リン酸、リン酸）、縮合リン酸、およびリンのオキソ酸または縮合リン酸とアルカリ金属またはアルカリ土類金属との塩のことをいい、これらの少なくとも１種以上を使用することができる。
例えば、リン酸類として亜リン酸、次亜リン酸、リン酸、ピロ燐酸、トリポリリン酸、ポリリン酸、ポリリン酸ナトリウム、ポリリン酸カリウム、ポリリン酸カリシウム、メタリン酸、ヘキサメタリン酸等が挙げられる。これらの中でも、ポリリン酸が最も好ましい。
また、リン酸類の好ましい濃度は０．１ｇ／Ｌ〜５０ｇ／Ｌであり、特に好ましくは０．５ｇ／Ｌ〜３０ｇ／Ｌである。
As used herein, phosphoric acid refers to phosphorus oxo acid (phosphorous acid, hypophosphorous acid, phosphoric acid), condensed phosphoric acid, and phosphorus oxo acid or condensed phosphoric acid and an alkali metal or alkaline earth metal. It refers to a salt, and at least one of these can be used.
Examples of phosphoric acids include phosphorous acid, hypophosphorous acid, phosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, sodium polyphosphate, potassium polyphosphate, potassium polyphosphate, metaphosphoric acid, hexametaphosphoric acid, and the like. Of these, polyphosphoric acid is most preferred.
Moreover, the preferable density | concentrations of phosphoric acid are 0.1 g / L-50 g / L, Most preferably, they are 0.5 g / L-30 g / L.
グリコール類とは、鎖式脂肪族炭化水素または環式脂肪族炭化水素の２つの炭素原子に１つずつヒドロキシ基が置換している構造を持つ化合物のことをいい、例えばエチレングリコール、プロピレングリコール、ジエチレングリコール等が挙げられ、中でもエチレングリコールが好ましい。グリコール類の好ましい濃度は０．０１ｇ／Ｌ〜５ｇ／Ｌであり、特に好ましくは０．０５ｇ／Ｌ〜３ｇ／Ｌである。 Glycols refer to compounds having a structure in which one hydroxy group is substituted for two carbon atoms of a chain aliphatic hydrocarbon or a cyclic aliphatic hydrocarbon, such as ethylene glycol, propylene glycol, Examples thereof include diethylene glycol, and ethylene glycol is preferable. The preferred concentration of glycols is 0.01 g / L to 5 g / L, particularly preferably 0.05 g / L to 3 g / L.
亜塩素酸塩系化成処理液のｐＨは、１０〜１４に設定することが好ましい。ｐＨを前記範囲に調整するためには、リン酸類以外の他の有機酸および／または無機酸およびこれらの可溶性の塩をさらに添加する。例えば、塩酸、硫酸、アルキルスルホン酸等が挙げられ、中でも塩酸が好ましい。 The pH of the chlorite-based chemical conversion treatment liquid is preferably set to 10-14. In order to adjust pH to the said range, other organic acids and / or inorganic acids other than phosphoric acids, and these soluble salts are further added. For example, hydrochloric acid, sulfuric acid, alkylsulfonic acid and the like can be mentioned, among which hydrochloric acid is preferable.
化成処理温度は、安定した品質維持するため２０〜１００℃が好ましい。なお、工業的規模での連続操業を考慮した場合、１００℃近い高温での生産においては、薬液の蒸発によるロスや、治具が劣化しやすくなる等コスト的に不利になるばかりか、頻繁な処理液濃度の管理を要する等、生産条件の管理が非常に難しくなり、品質の安定性に悪影響を及ぼす可能性が生じるため、処理液温度として２５〜６５℃が最も好ましい。 The chemical conversion treatment temperature is preferably 20 to 100 ° C. in order to maintain stable quality. In consideration of continuous operation on an industrial scale, production at a high temperature close to 100 ° C. is not only disadvantageous in terms of cost, such as loss due to evaporation of chemicals, and jigs being prone to deterioration. Since the management of the production conditions becomes very difficult, for example, the management of the processing liquid concentration is required, and there is a possibility of adversely affecting the stability of the quality, the processing liquid temperature is most preferably 25 to 65 ° C.
化成処理時間は、銅系金属の種類、銅系金属表面の酸化膜の厚さおよび状態、後処理の有無、前処理条件等、本件処理前の銅系金属の表面の状態や化成処理液の組成および処理温度等によって最適な処理時間は大きく変化する。よって、本発明においては化成処理時間は特に限定されず、目視により銅系金属表面が所望の色調となる最適な処理時間を選択することが可能であるが、生産性の観点から処理時間としては、１０秒〜６０分が好ましく、最も好ましくは、１５秒〜３０分である。 The chemical treatment time is the type of copper-based metal, the thickness and state of the oxide film on the surface of the copper-based metal, the presence / absence of post-treatment, pre-treatment conditions, etc. The optimum processing time varies greatly depending on the composition and processing temperature. Therefore, in the present invention, the chemical conversion treatment time is not particularly limited, and it is possible to select an optimal treatment time for which the copper-based metal surface has a desired color tone by visual observation, but from the viewpoint of productivity, the treatment time is It is preferably 10 seconds to 60 minutes, and most preferably 15 seconds to 30 minutes.
本発明における青色の色調とは、色調をマンセル表色系で表した場合、その色相（Ｈ）がＧＹ（黄緑）、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、青紫（ＰＢ）、紫（Ｐ）の色相に分類されるものをいい。好ましくは、Ｇ（緑）、ＢＧ（青緑）、Ｂ（青）、青紫（ＰＢ）の色相に分類されるものをいい、最も好ましくは、ＢＧ（青緑）、Ｂ（青）、青紫（ＰＢ）に分類されるものをいう。 In the present invention, the blue color tone means that when the color tone is expressed in the Munsell color system, the hue (H) is GY (yellowish green), G (green), BG (blue green), B (blue), blue purple ( Those classified into hues of PB) and purple (P). Preferred are those classified into hues of G (green), BG (blue green), B (blue), and bluish purple (PB), and most preferred are BG (blue green), B (blue), blue purple ( Those classified as PB).
さらに、好ましくはマンセル表色系で表した場合の明度（Ｖ）が２以上８．５以下、彩度（Ｃ）が２以上のものであり、より好ましくは、マンセル表色系における明度（Ｖ）が２．５以上７以下、彩度（Ｃ）は４以上のものである。 Furthermore, the lightness (V) when expressed in the Munsell color system is preferably 2 or more and 8.5 or less, and the saturation (C) is 2 or more, more preferably the lightness (V) in the Munsell color system. ) Is 2.5 or more and 7 or less, and the saturation (C) is 4 or more.
上述の本願発明による化成処理薬液および化成処理条件による処理方法を、以下「青染め化成処理」と略記することがある。
本発明で使用する化成処理液は、銅系金属にのみ効果を有し、その他の鉄、ステンレス等の鉄系金属では効果が得られず、銅系金属に最も適した青染め化成処理液である。
本発明における銅系金属とは、少なくともその最表面が銅系金属により形成されているものであればよく、例えば鋳造、鍛造、圧延、プレス等により製造されたバルクそのものが銅系金属よりなるもの、あるいは、めっき等により最表面が銅系金属皮膜により形成されている物等、少なくともその最表面が銅系金属により形成されてさえいれば、本願発明に含まれる。
The treatment method using the chemical conversion treatment liquid and the chemical treatment conditions according to the present invention described above may be abbreviated as “blue dyeing chemical conversion treatment” hereinafter.
The chemical conversion treatment solution used in the present invention is effective only for copper-based metals, and is not effective with other iron-based metals such as iron and stainless steel. is there.
In the present invention, the copper-based metal may be any metal as long as the outermost surface is formed of a copper-based metal. For example, a bulk produced by casting, forging, rolling, pressing, or the like is made of a copper-based metal. Alternatively, it is included in the present invention as long as at least the outermost surface is formed of a copper-based metal, such as a product whose outermost surface is formed of a copper-based metal film by plating or the like.
本発明の処理方法の対象となる銅系金属としては、銅を主成分とする金属であれば特に限定されるものではないが、銅、銅−錫系合金、銅−亜鉛系合金がより好ましい。
中でも、通電可能な素材（例えば、鉄、鋼、銅、真鍮等の金属素材、あるいはセラミックあるいはプラスチック素材に予めなんらかの金属めっきが施されたもの等）に後述する銅系の金属めっきを施したもの、あるいは製品素材（バルク）自体が銅または真鍮（銅−亜鉛系合金）である鍛造品、鋳造品、圧延プレス品等が最も好ましい。
Although it will not specifically limit if it is a metal which has copper as a main component as a copper metal used as the object of the processing method of the present invention, copper, a copper-tin alloy, and a copper-zinc alloy are more preferred. .
Among them, materials that can be energized (for example, metal materials such as iron, steel, copper, brass, etc., or those in which some metal plating has been applied in advance to a ceramic or plastic material, etc.) have been subjected to copper-based metal plating described later. Alternatively, a forged product, a cast product, a rolled press product or the like in which the product material (bulk) itself is copper or brass (copper-zinc alloy) is most preferable.
銅系の金属めっきとは、めっき浴中に少なくとも銅イオンを含有しためっき浴を使用して、公知のめっき技術により電気めっきを行うことにより皮膜形成されたものをいう。
銅系の電気めっき浴としては、硫酸塩浴、シアン浴、ピロ燐酸塩浴等各種あるが、本発明では、いずれのめっき浴も使用可能である。但し、服飾品、装飾品で扱われる物には小物部品が多く、生産性の観点からバレルめっきでめっきが行われるのが主流であること、かつシアン浴は有毒であり作業者への負荷が大きいこと等より、本発明のめっき浴としては、特にピロ燐酸塩浴による銅めっき浴がより好ましい。
Copper-based metal plating refers to a film formed by electroplating by a known plating technique using a plating bath containing at least copper ions in a plating bath.
There are various types of copper-based electroplating baths, such as a sulfate bath, a cyan bath, and a pyrophosphate bath. In the present invention, any plating bath can be used. However, there are many small parts in the items handled in clothing and ornaments, and from the viewpoint of productivity, barrel plating is the mainstream, and the cyan bath is toxic and burdens on workers. Because of its large size, the plating bath of the present invention is particularly preferably a copper plating bath using a pyrophosphate bath.
本願発明の表面が青色の色調を有する銅系金属の製造方法としては、少なくとも本願発明の青染め化成処理方法を必須工程として備えていればよく、その他に、銅系めっき浴を使用した電気めっき工程、脱脂工程、水洗工程、活性化処理工程、乾燥工程等を必要に応じて適宜導入すればよい。 As a method for producing a copper-based metal having a blue tone on the surface of the present invention, it is sufficient that at least the blue-dyed chemical conversion treatment method of the present invention is provided as an essential step, and in addition, electroplating using a copper-based plating bath What is necessary is just to introduce | transduce a process, a degreasing process, a water washing process, an activation process process, a drying process, etc. suitably as needed.
さらに、銅系めっき工程より前であれば、他の金属めっき処理を行ってもよいし、青染め化成処理工程の前後いずれかの工程で変色防止処理等の他の化成処理工程を導入したり、青染め化成処理後に、さらにニス等によるクリア塗装および／または顔料または染料が含まれる他の有機系塗料による着色塗装等の塗装処理（コーティング処理）工程を設けることも、本発明の効果を害しないかぎり可能である。 Furthermore, if it is before the copper plating process, other metal plating treatments may be performed, or other chemical conversion treatment processes such as discoloration prevention treatment may be introduced at any step before or after the blue dyeing chemical conversion treatment process. In addition, after the blue dyeing conversion treatment, it is also possible to provide a painting treatment (coating treatment) step such as clear painting with varnish and / or colored painting with other organic paint containing pigment or dye. It is possible unless it is done.
なお、銅系めっき工程と青染め化成処理工程をオフラインで行う場合、または銅系めっき工程での銅系めっき後から青染め化成処理工程までにかなりの時間が空く場合は、めっき処理後に、銅系金属の変色、腐食を防止するために、変色防止剤、防錆剤等による化成処理および／または防錆処理を実施することが好ましい。 If the copper plating process and the blue dyeing conversion treatment process are performed off-line, or if a considerable amount of time is left between the copper plating in the copper plating process and the blue dyeing conversion treatment process, In order to prevent discoloration and corrosion of the system metal, it is preferable to carry out a chemical conversion treatment and / or a rust prevention treatment with a discoloration inhibitor, a rust inhibitor, or the like.
変色防止剤としては、銅系金属用の市販の変色防止剤等適宜選択可能である。例えば、ベンゾトリアゾ−ル系変色防止剤であるアイガード２０４０（株式会社アイコー製）、ＶＥＲＺＯＮＥ ＳＦ−３１０（大和化成株式会社製）等が挙げられる。
なお、青染め化成処理前に変色防止剤、防錆剤等による化成処理および／または防錆処理が実施されている場合は、青染め化成処理を行う前に、アルカリ系薬液による脱脂処理、および／または酸系薬液による活性化処理を実施することが外観の均一性、青色の発色の観点から好ましい。
As the discoloration preventing agent, a commercially available discoloration preventing agent for copper-based metals can be appropriately selected. For example, eye guard 2040 (manufactured by Aiko Co., Ltd.) and VERZONE SF-310 (manufactured by Yamato Kasei Co., Ltd.), which are benzotriazole-based discoloration inhibitors, can be used.
In addition, before the blue dyeing conversion treatment, if the chemical conversion treatment and / or rust prevention treatment with a discoloration prevention agent, a rust preventive agent, etc. is carried out, the degreasing treatment with an alkaline chemical solution, and It is preferable to perform an activation treatment with an acid chemical solution from the viewpoints of appearance uniformity and blue color development.
本願発明による青色の色調を有した製品の適用用途としては、ブローチ、ボタン、バックル、ファスナー、カフスボタン等の衣類に使用される服飾品、ネックレス、イアリング等の装飾品、玩具、電子・電気部品等およびその他工業用品等に好適に適用される。中でも、服飾品、装飾品への用途への適用が最も好適に適用される。 Applicable uses of products having a blue color tone according to the present invention include clothing used for clothing such as brooches, buttons, buckles, fasteners, cufflinks, ornaments such as necklaces and earrings, toys, electronic / electrical parts And other industrial articles. Among these, application to apparel and ornaments is most preferably applied.
以下に、試験例、実施例および比較例を挙げて本発明を説明するが、本発明は以下の記載により限定されるものではない。 Hereinafter, the present invention will be described with reference to test examples, examples and comparative examples, but the present invention is not limited to the following description.
銅めっき製品：
実施例および比較例で使用する銅めっき製品を下記により作成した。
真鍮（黄銅）製のボタントップパーツ部材（品名「Ｂ２７Ｓ．プレーン」）を適量バレルに投入し、浸漬脱脂（ソフィアクリーナー１１００（日本ニュークローム（株））：６０ｇ／Ｌ ５０℃、１２分）を行い、さらに電解脱脂（ソフィアクリーナー１１００（日本ニュークローム（株））：１００ｇ／Ｌ、５０℃、５Ｖ、１２分）、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で５分浸漬後、水洗を行い、下記の銅めっき浴（１）中で５０℃、電流密度０．１Ａ／ｄｍ2で３０分間めっきを行った後、水洗後、カゴに移し、ＶＥＲＺＯＮＥ ＳＦ−３１０（大和化成（株））５０ｍｌ／Ｌ溶液に３０秒浸漬後、水洗し、メタノール浸漬後に乾燥を行い、最表面が銅よりなる銅めっき製品を作成した。
Copper plating products:
The copper plating products used in the examples and comparative examples were prepared as follows.
An appropriate amount of a brass (brass) button top part member (product name “B27S.Plain”) is put into a barrel and immersed and degreased (Sophia Cleaner 1100 (Nippon New Chrome Co., Ltd.): 60 g / L, 50 ° C., 12 minutes). Further, electrolytic degreasing (Sofia Cleaner 1100 (Nippon New Chrome Co., Ltd.): 100 g / L, 50 ° C., 5 V, 12 minutes) and washing with water were performed. Then, after immersing in commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 5 minutes, washing with water and plating in the following copper plating bath (1) at 50 ° C. and current density of 0.1 A / dm 2 for 30 minutes. After rinsing with water, it is transferred to a basket, immersed in a 50 ml / L solution of VERZONE SF-310 (Daiwa Kasei Co., Ltd.) for 30 seconds, washed with water, dried after immersing in methanol, and the outermost surface of copper made of copper. A plated product was created.
銅めっき浴（１）
ピロ燐酸カリウム：３９０ｇ／Ｌ、
ピロ燐酸銅：９０ｇ／Ｌ、
ピロトップＰＣ（奥野製薬工業（株）製）：１．５ｍｌ／Ｌ。
Copper plating bath (1)
Potassium pyrophosphate: 390 g / L,
Copper pyrophosphate: 90 g / L,
Pyrotop PC (Okuno Pharmaceutical Co., Ltd.): 1.5 ml / L.
実施例１：
銅めっき製品を浸漬処理用の治具（またはカゴ）に適量投入し、浸漬脱脂（アイクリーン１２３０（（株）アイコー）４０ｇ／Ｌ、５０℃〜６０℃、２分）し水洗後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して、実施例１の製品を得た。その後得られた製品に下記の外観判定を行った。その結果を合わせて表１に示す。
Example 1:
An appropriate amount of copper-plated product is put into a jig (or basket) for immersion treatment, immersion degreasing (eye clean 1230 (Aiko Co., Ltd.) 40 g / L, 50 ° C. to 60 ° C., 2 minutes), washed with water, and then commercially available hydrochloric acid (35% HCl) Soaked in 100 ml / L solution at room temperature for 30 seconds, washed with water, soaked with the blue dyeing chemical treatment solution and treatment conditions shown in Table 1, washed with water and dried to obtain the product of Example 1. Obtained. Thereafter, the following appearance determination was performed on the obtained product. The results are shown in Table 1.
外観判定
目視により、サンプルを下記の「マンセルシステムによる色彩の定規」に掲載されている色票と直接比較し、その色票の中でサンプルの色調に最も近い色票をそのサンプルの色調とし、このマンセル表色系で表し、その色相（Ｈ）をもとに下記の「◎，○，×」の３段階の基準で評価した。
評価基準：
◎：色相（Ｈ）がＧ（緑）、ＢＧ（青緑）、Ｂ（青）、青紫（ＰＢ）のいずれか、
○：色相（Ｈ）がＧＹ（黄緑）、紫（Ｐ）のいずれか、
×：上記以外の色相。
使用した色票：
マンセルシステムによる色彩の定規（拡充版）(発行：日本色研事業株式会社)
［色の内容］
色相数：２４色相（５Ｒ、７．５Ｒ、１０Ｒ、２．５ＹＲ、５ＹＲ、７．５ＹＲ、１０ＹＲ、２．５Ｙ、５Ｙ、１０Ｙ、５ＧＹ、１０ＧＹ、５Ｇ、１０Ｇ、５ＢＧ、１０ＢＧ、５Ｂ、１０Ｂ、５ＰＢ、１０ＰＢ、５Ｐ、１０Ｐ、５ＲＰ、１０ＲＰ）、
明度段階：９段階（無彩色のみ１８段階）
彩度段階：０、１、２、３、４、６、８、１０、１２、１４
色数：有彩色１０７１色、無彩色１８段階
Appearance judgment Visually compare the sample directly with the color chart published in the following `` Color ruler by Munsell system '', and the color chart closest to the sample color tone among the color charts is the color tone of the sample, This is expressed in the Munsell color system and evaluated based on the hue (H) based on the following three grades “◎, ○, ×”.
Evaluation criteria:
A: Hue (H) is one of G (green), BG (blue green), B (blue), and bluish purple (PB),
○: Hue (H) is either GY (yellowish green) or purple (P),
X: Hue other than the above.
Color chart used:
Color ruler by Munsell system (enlarged version) (Published by Nippon Color Research Co., Ltd.)
[Color contents]
Number of hues: 24 hues (5R, 7.5R, 10R, 2.5YR, 5YR, 7.5YR, 10YR, 2.5Y, 5Y, 10Y, 5GY, 10GY, 5G, 10G, 5BG, 10BG, 5B, 10B, 5PB, 10PB, 5P, 10P, 5RP, 10RP),
Lightness level: 9 levels (18 levels only for achromatic colors)
Saturation stage: 0, 1, 2, 3, 4, 6, 8, 10, 12, 14
Number of colors: 1071 chromatic colors, 18 achromatic colors
実施例２〜３：
青染め化成処理条件が異なる以外は、実施例１と同様の方法で実施し、実施例２、３の製品を作成した。実施した青染め化成処理条件を表１に示す。その後得られた製品の外観判定を実施例１と同様に行った。その結果も合わせて表１に示す。
Examples 2-3:
The products of Examples 2 and 3 were prepared in the same manner as in Example 1 except that the blue dyeing conversion treatment conditions were different. Table 1 shows the blue dyeing conversion treatment conditions that were performed. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例４：
銅めっき製品を浸漬処理用の治具（またはカゴ）に適量投入し、浸漬脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：５０ｇ／Ｌ ５０℃、２分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して実施例４の製品を作成した。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 4:
Put an appropriate amount of copper-plated product into a jig (or basket) for immersion treatment, perform immersion degreasing (Sophia Cleaner 1100 (Japan New Chrome Co., Ltd.): 50 g / L, 50 ° C., 2 minutes), and wash with water. went. Then, after being immersed in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 30 seconds, washed with water, immersed in the blue dyeing chemical treatment solution and processing conditions shown in Table 1, washed with water and dried, Example 4 Created a product. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例５：
使用した青染め化成処理液および処理条件が異なる以外は、実施例４と同様の方法で実施し、実施例５の製品を作成した。使用した青染め化成処理液および処理条件を表１に示す。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 5:
The product of Example 5 was prepared in the same manner as in Example 4 except that the blue dyeing conversion treatment solution and the processing conditions used were different. Table 1 shows the blue dyeing conversion liquid used and the processing conditions. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例６：
銅めっき製品を適量、処理用の治具（またはカゴ）に投入し、電解脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：５０ｇ／Ｌ ５０℃、１Ａ、１分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して実施例６の製品を作成した。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 6:
An appropriate amount of copper-plated product is put into a processing jig (or basket), and electrolytic degreasing (Sophia Cleaner 1100 (Japan New Chrome Co., Ltd.): 50 g / L 50 ° C., 1 A, 1 minute) is performed. Washed with water. Then, after being immersed in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 30 seconds, washed with water, immersed in the blue dyeing chemical treatment solution and processing conditions shown in Table 1, washed with water and dried, Example 6 Created a product. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例７：
真鍮（黄銅）製のボタンのトップパーツ部材（品名「Ｂ２７Ｓ．プレーン」）を適量、浸漬処理用の治具（またはカゴ）に投入し、浸漬脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：８０ｇ／Ｌ ５０℃、２分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で６０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して実施例７の製品を作成した。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 7:
An appropriate amount of a top part member (product name “B27S.Plain”) made of brass (brass) is put into a jig (or basket) for immersion treatment, and immersion degreasing (Sophia Cleaner 1100 (Nippon New Chrome Co., Ltd.) )): 80 g / L 50 ° C., 2 minutes), and washed with water. Then, after immersing in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 60 seconds, it was washed with water, immersed in the blue dyeing chemical treatment solution and processing conditions shown in Table 1, washed with water and dried. Created a product. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例８：
使用した青染め化成処理液および処理条件が異なる以外は、実施例６と同様の方法で実施し、実施例８の製品を作成した。使用した青染め化成処理液および処理条件を表１に示す。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 8:
The product of Example 8 was prepared in the same manner as in Example 6 except that the blue dyeing chemical treatment solution and the processing conditions used were different. Table 1 shows the blue dyeing conversion liquid used and the processing conditions. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例９：
真鍮（黄銅）製のボタンのトップパーツ部材（品名「Ｂ２７Ｓ．プレーン」）を適量、処理用の治具（またはカゴ）に投入し、電解脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：５０ｇ／Ｌ ５０℃、１Ａ、１分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して実施例９の製品を作成した。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
＊本実施例では、薬液の蒸発量がかなり多く（約３時間で約１２０ｍＬ程度蒸発）、連続的な生産をする場合、品質の維持のために薬液の頻繁な調整管理を要すると考えられる。また、薬液コスト的に不利である。
Example 9:
An appropriate amount of a top part member (product name “B27S.Plain”) made of brass (brass) is placed in a processing jig (or basket), and electrolytic degreasing (Sophia Cleaner 1100 (Nippon New Chrome Co., Ltd.) ): 50 g / L 50 ° C., 1 A, 1 minute) and washed with water. Then, after being immersed in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 30 seconds, washed with water, immersed in the blue dyeing chemical treatment solution and processing conditions shown in Table 1, washed with water and dried. Created a product. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
* In this example, the amount of evaporation of the chemical solution is considerably large (about 120 mL evaporation in about 3 hours), and it is considered that frequent adjustment and management of the chemical solution is required to maintain the quality in the case of continuous production. Moreover, it is disadvantageous in terms of chemical cost.
実施例１０：
使用した青染め化成処理液および処理条件が異なる以外は、実施例９と同様の方法で実施し、実施例１０の製品を作成した。使用した青染め化成処理液および処理条件を表１に示す。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 10:
The product of Example 10 was prepared in the same manner as in Example 9 except that the blue dyeing conversion treatment solution and the processing conditions used were different. Table 1 shows the blue dyeing conversion liquid used and the processing conditions. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例１１：
青染め化成処理条件が異なる以外は、実施例１と同様の方法で実施し、実施例１１の製品を作成した。実施した青染め化成処理条件を表１に示す。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 11:
The product of Example 11 was prepared in the same manner as in Example 1 except that the blue dyeing conversion treatment conditions were different. Table 1 shows the blue dyeing conversion treatment conditions that were performed. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例１２〜１３：
使用した青染め化成処理液および処理条件が異なる以外は、実施例６と同様の方法で実施し、実施例１２、１３の製品を作成した。使用した青染め化成処理液および処理条件を表１に示す。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Examples 12-13:
The products of Examples 12 and 13 were prepared in the same manner as in Example 6 except that the blue dyeing conversion treatment solution and the processing conditions used were different. Table 1 shows the blue dyeing conversion liquid used and the processing conditions. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
実施例１４：
使用した青染め化成処理液および処理条件が異なる以外は、実施例９と同様の方法で実施し、実施例１４の製品を作成した。使用した青染め化成処理液および処理条件を表１に示す。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Example 14:
The product of Example 14 was prepared in the same manner as in Example 9 except that the blue dyeing conversion treatment solution and the processing conditions used were different. Table 1 shows the blue dyeing conversion liquid used and the processing conditions. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
比較例１〜２：
青染め化成処理条件が異なる以外は、実施例１と同様の方法で実施し、比較例１、２の製品を作成した。実施した青染め化成処理条件を表１に示す。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Comparative Examples 1-2:
Except that the blue dyeing conversion treatment conditions were different, the same method as in Example 1 was carried out to produce products of Comparative Examples 1 and 2. Table 1 shows the blue dyeing conversion treatment conditions that were performed. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
比較例３〜４：
真鍮（黄銅）製のボタンのトップパーツ部材（品名「Ｂ２７Ｓ．プレーン」）を浸漬処理用の治具（またはカゴ）に適量投入し、浸漬脱脂（アイクリーン１２３０（（株）アイコー）４０ｇ／Ｌ、５０℃〜６０℃、２分）し水洗後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して、比較例３、４の製品を得た。その後得られた製品に下記の外観判定を行った。その結果を合わせて表１に示す。
Comparative Examples 3-4:
An appropriate amount of a top part member (product name “B27S.Plain”) made of brass (brass) is put into a jig (or basket) for immersion treatment, and immersion degreasing (Eye Clean 1230 (Aiko Co., Ltd.) 40 g / L 50 ° C. to 60 ° C., 2 minutes), washed with water, immersed in 100 ml / L of commercial hydrochloric acid (35% HCl) at room temperature for 30 seconds, washed with water, and subjected to the blue dyeing chemical treatment solution and treatment conditions shown in Table 1. The products of Comparative Examples 3 and 4 were obtained by dipping, washing with water and drying. Thereafter, the following appearance determination was performed on the obtained product. The results are shown in Table 1.
比較例５：
ハルセル陰極板（鉄）（（株）山本鍍金試験器）を使用し、ハルセル陰極板(鉄)表面に予め施されている亜鉛めっきを適宜酸洗により除去し、鉄表面を露出させた後、浸漬脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：５０ｇ／Ｌ ５０℃、２分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して比較例５の製品を作成した。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Comparative Example 5:
After using a Hull cell cathode plate (iron) (Yamamoto plating tester Co., Ltd.), the zinc plating previously applied to the Hull cell cathode plate (iron) surface was appropriately removed by pickling, and the iron surface was exposed. Immersion degreasing (Sofia Cleaner 1100 (Nippon New Chrome Co., Ltd.): 50 g / L, 50 ° C., 2 minutes) was performed, followed by washing with water. Then, after being immersed in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 30 seconds, it was washed with water, immersed in the blue dyeing chemical treatment solution and processing conditions shown in Table 1, washed with water and dried. Created a product. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
比較例６：
ハルセル陰極板（ＳＵＳ３０４）（（株）山本鍍金試験器）を使用し、浸漬脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：５０ｇ／Ｌ ５０℃、２分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗を行い、表１に示す青染め化成処理液および処理条件で浸漬処理し、水洗、乾燥して比較例６の製品を作成した。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Comparative Example 6:
Using a Hull cell cathode plate (SUS304) (Yamamoto plating tester Co., Ltd.), immersion degreasing (Sophia Cleaner 1100 (Nippon New Chrome Co., Ltd.): 50 g / L, 50 ° C., 2 minutes) is performed and washed with water. went. Then, after being immersed in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 30 seconds, washed with water, immersed in the blue dyeing chemical treatment solution and the treatment conditions shown in Table 1, washed with water and dried, then Comparative Example 6 Created a product. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
比較例７：
銅めっき製品を適量、処理用の治具（またはカゴ）に投入し、電解脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：５０ｇ／Ｌ ５０℃、１Ａ、１分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗、乾燥して、比較例７の製品を得た。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Comparative Example 7:
An appropriate amount of copper-plated product is put into a processing jig (or basket), and electrolytic degreasing (Sophia Cleaner 1100 (Japan New Chrome Co., Ltd.): 50 g / L 50 ° C., 1 A, 1 minute) is performed. Washed with water. Then, after being immersed in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 30 seconds, washed with water and dried, a product of Comparative Example 7 was obtained. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
比較例８：
真鍮（黄銅）製のボタンのトップパーツ部材（品名「Ｂ２７Ｓ．プレーン」）を適量、処理用の治具（またはカゴ）に投入し、電解脱脂（ソフィアクリ−ナー１１００（日本ニュークローム（株））：５０ｇ／Ｌ ５０℃、１Ａ、１分）を行い、水洗を行った。その後、市販塩酸（３５％ＨＣｌ）１００ｍｌ／Ｌ溶液に室温で３０秒浸漬後、水洗、乾燥して、比較例８の製品を得た。その後得られた製品の外観判定を、実施例１と同様に行った。その結果も合わせて表１に示す。
Comparative Example 8:
An appropriate amount of a top part member (product name “B27S.Plain”) made of brass (brass) is placed in a processing jig (or basket), and electrolytic degreasing (Sophia Cleaner 1100 (Nippon New Chrome Co., Ltd.) ): 50 g / L 50 ° C., 1 A, 1 minute) and washed with water. Thereafter, it was immersed in a commercial hydrochloric acid (35% HCl) 100 ml / L solution at room temperature for 30 seconds, washed with water and dried to obtain a product of Comparative Example 8. Thereafter, the appearance of the obtained product was determined in the same manner as in Example 1. The results are also shown in Table 1.
Claims (10)
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| JP2016079506A (en) * | 2014-10-10 | 2016-05-16 | 日本ニュークローム株式会社 | Treatment method for coloring surface in rainbow color |
| WO2018142487A1 (en) | 2017-01-31 | 2018-08-09 | Ykk株式会社 | Article having metallic surface, tone-treatment method therefor, and gas phase oxidation device |
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