JPS63277797A - Composite plating method - Google Patents
Composite plating methodInfo
- Publication number
- JPS63277797A JPS63277797A JP11398087A JP11398087A JPS63277797A JP S63277797 A JPS63277797 A JP S63277797A JP 11398087 A JP11398087 A JP 11398087A JP 11398087 A JP11398087 A JP 11398087A JP S63277797 A JPS63277797 A JP S63277797A
- Authority
- JP
- Japan
- Prior art keywords
- silane coupling
- coupling agent
- plating
- particles
- nonionic surfactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007747 plating Methods 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 12
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 11
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 5
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims abstract description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 20
- 229910000831 Steel Inorganic materials 0.000 abstract description 12
- 239000010959 steel Substances 0.000 abstract description 12
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000843 powder Substances 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 abstract 1
- 239000010954 inorganic particle Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000004780 naphthols Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- -1 γ-glycidoxypropyl methyl Chemical group 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は複合めっき法に関し、さらに詳しくは、耐蝕性
、塗装性に優れた複合めっき法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a composite plating method, and more particularly to a composite plating method with excellent corrosion resistance and paintability.
し従来技術］
従来より、めっき皮膜に耐蝕性を付与する目的で、亜鉛
、カドミウム等の犠牲溶解型のめっき皮膜が工業的に用
いられている。BACKGROUND ART Conventionally, sacrificial dissolution type plating films of zinc, cadmium, etc. have been used industrially for the purpose of imparting corrosion resistance to the plating film.
亜鉛めっき鋼板においては、さらに耐蝕性を改善すべ（
ＦｅＳＮｉＳＣｏ、Ｍｎ等を合金化させためっき、アル
ミニウム粉末を分散させたＺｎ−Ａｌ複合めっき（特許
第９９４９４４号明細書）、Ｓｉｎ、を分散させたＺｎ
５ｔｙｘ複合めっき（特公昭５６−０４９９９９号
公報）、Ｚｎ−Ｆｅ、Ｎ１５Ｃｏ−無機物複合めっき（
特公昭６２−００６７６０号公報）等が開発されている
。The corrosion resistance of galvanized steel sheets should be further improved (
FeSNiSCo, plating alloyed with Mn, etc., Zn-Al composite plating with dispersed aluminum powder (Patent No. 994944 specification), Zn with dispersed Sin.
5tyx composite plating (Japanese Patent Publication No. 56-049999), Zn-Fe, N15Co-inorganic composite plating (
Japanese Patent Publication No. 62-006760) etc. have been developed.
しかして、Ｚｎ−無機物複合めっきでは分散剤である５
ｔｙｘ、’ｒｉｏｔ、Ｚｒ０ｔがめつき、釜中で負に帯
電するため、陰極となるめっき面には移動せず共析し難
いという欠点がある。そして、負に帯電した無機物をめ
っき皮膜中に共析させるためには、浴中の無機物濃度を
高濃度とし、高電流密度でめっきを行なう必要があり、
浴の寿命低下、亜鉛のクーロン効率低下、複合めっき皮
膜組成の不安定等の問題がある。However, in Zn-inorganic composite plating, 5, which is a dispersant,
Since tyx, 'riot, and Zr0t are plated and negatively charged in the pot, they do not move to the plated surface that becomes the cathode and are difficult to eutectoid. In order to eutectoid negatively charged inorganic substances into the plating film, it is necessary to increase the concentration of inorganic substances in the bath and perform plating at high current density.
There are problems such as reduced bath life, reduced coulombic efficiency of zinc, and instability of the composite plating film composition.
また、Ｚｎ−Ｆｅ、Ｎｉ、Ｃｏ−無機物複合めっきでは
、Ｆｅ”中、Ｎｉ”％ Ｃｏ”がめつき浴中で負に帯電
している無機物に吸若し、正電荷を与えるため無機物は
共析し易くなると言われているが（特公昭６２−００６
７６０号公報）、充分なＳｉｎ。In addition, in Zn-Fe, Ni, Co-inorganic composite plating, Fe (Ni)% Co adsorbs negatively charged inorganic materials in the plating bath and gives them a positive charge, so the inorganic materials eutectoid. It is said that it becomes easier to
No. 760), sufficient Sin.
共析１を得るためには浴中の無機物、Ｆ ｅ”、Ｎｉ”
、Ｃｏ’？ ６度を高濃度にする必要があり、その結果
、浴中の無機物の２次凝集、即ち、めっき皮膜中の無機
物粒子の不均一等の問題がある。In order to obtain eutectoid 1, inorganic substances in the bath, Fe", Ni"
,Co'? It is necessary to have a high concentration of 6°C, and as a result, there are problems such as secondary aggregation of inorganic substances in the bath, that is, non-uniformity of inorganic particles in the plating film.
［発明が解決しようとする問題点］
本発明は上記に説明したように、従来における複合めっ
き鋼板が有する種々の問題点に鑑み、本発明者が鋭意研
究を行ない、検討を重ねノρ結果、高濃度の電解質を有
するめっき浴中において無機物粒子を安定に分散させる
ことができ、さらに、少量の無機物共析により耐蝕性、
塗装性を向上させることができる複合めっき法を開発し
たのである。[Problems to be Solved by the Invention] As explained above, the present invention has been made in view of the various problems that conventional composite plated steel sheets have, and as a result of intensive research and repeated consideration. Inorganic particles can be stably dispersed in a plating bath with a high concentration of electrolyte, and corrosion resistance and
They developed a composite plating method that can improve paintability.
［問題点を解決するための手段］
本発明に係る複合めっき法の特徴とするところは、粒径
０．１μｍ以下のＳｔｏｗ、Ｔｉｅ、、Ｚｒ０ｔ−Ｔａ
ｔＯｓの１種または２種以上を非イオン界面活性剤およ
びシランカップリング剤を含む液中で処理後、亜鉛或い
は亜鉛とニッケル、鉄、コバルト、マンガンの１種また
は２種以上の合金めっき液中に添加し、電解処理するこ
とにある。[Means for Solving the Problems] The composite plating method according to the present invention is characterized in that Stow, Tie, Zr0t-Ta with a particle size of 0.1 μm or less
After treating one or more types of tOs in a solution containing a nonionic surfactant and a silane coupling agent, in a plating solution containing zinc or one or more alloys of zinc and nickel, iron, cobalt, and manganese. The purpose is to add it to the water and electrolytically treat it.
なお、非イオン界面活性剤が、ナフトール誘導体であり
、シランカップリング剤は無機物と化学結合する反応基
がメトキシ基或いはエトキシ基で、有機物と化学結合す
る反応基がアミノ基またはエポキシ基を含むものである
。The nonionic surfactant is a naphthol derivative, and the silane coupling agent has a methoxy or ethoxy group as a reactive group that chemically bonds with an inorganic substance, and an amino group or an epoxy group as a reactive group that chemically bonds with an organic substance. .
本発明に係る複合めっき法は、粒径０．１μｍ以下のＳ
ｔｏｗ、Ｔ ｉ Ｏｔ、Ｚｒ０ｔＳＴａ＊Ｏｓの１種ま
たは２種以上を非イオン界面活性剤およびシランカップ
リング剤を含む液中で処理後、亜鉛或いは亜鉛とニッケ
ル、鉄、コバルト、マンガンのｌＦｌ！または２種以上
の合金めっき液中に添加し、電解処理することにより、
シランカップリング剤と化学結合した上記無機物粒子を
均一に分散させた複合めっき鋼板を製造することができ
る。The composite plating method according to the present invention uses S with a particle size of 0.1 μm or less.
After treating one or more of tow, T i Ot, and Zr0tSTa*Os in a solution containing a nonionic surfactant and a silane coupling agent, zinc or zinc and nickel, iron, cobalt, and manganese lFl! Or by adding it to two or more alloy plating solutions and electrolytically treating it,
A composite plated steel sheet can be produced in which the above-mentioned inorganic particles chemically bonded to a silane coupling agent are uniformly dispersed.
このようにして、製造された複合めっき鋼板は少量の無
機物粒子共析にも拘わらず非常に優れた耐蝕性および塗
装性を有しているものである。The composite plated steel sheet produced in this way has excellent corrosion resistance and paintability despite a small amount of eutectoid inorganic particles.
本発明に係る複合めっき法について、以下詳細に説明す
る。The composite plating method according to the present invention will be explained in detail below.
本発明に係る複合めっき法においては、酸性水溶液中で
安定なゾルを形成し、微粒子状で金属イオンが吸着し易
く、かつ、シランカップリング処理できる無機物粒子と
しては、Ｓ ｉ Ｏｔ、Ｔｉ１ｔ、Ｚｒ０ｔ、Ｔａｘｅ
ｓを使用するのである。In the composite plating method according to the present invention, inorganic particles that form a stable sol in an acidic aqueous solution, are fine particles that easily adsorb metal ions, and can be subjected to silane coupling treatment include SiOt, Ti1t, and Zr0t. ,Taxe
s is used.
このような、無機物粒子の粒径は０．１μｍ以下であり
、０．１μｍ以上では液中で沈降し易く、また、めっき
皮膜の密着性が悪くなる。The particle size of such inorganic particles is 0.1 μm or less, and if it is 0.1 μm or more, they tend to settle in the liquid and the adhesion of the plating film deteriorates.
また、めっき皮膜中の無機物の分散を均一にする浴中の
界面活性剤としては、非イオン界面活性剤であるナフト
ール誘導体を使用するのがよい。Further, as a surfactant in the bath for uniformly dispersing inorganic substances in the plating film, it is preferable to use a naphthol derivative, which is a nonionic surfactant.
そして、シランカップリング剤は、無機物と化学結合す
る反応基がメトキシ基或いはエトキシ基で、有機物と化
学結合する反応基がアミノ基またはエポキシ基を含むも
ので、耐蝕性および塗装性に良好な結果が得られた。例
えば、γ−グリシドキシプロビルメチルジェトキシシラ
ン、γ−アミノプロピルメチルジメトキシシラン等が使
用できる。The silane coupling agent has a methoxy or ethoxy group as a reactive group that chemically bonds with inorganic substances, and an amino group or epoxy group as a reactive group that chemically bonds with organic substances, resulting in good corrosion resistance and paintability. was gotten. For example, γ-glycidoxypropylmethyljethoxysilane, γ-aminopropylmethyldimethoxysilane, etc. can be used.
本発明に係る複合めっき法において、めっき液の製造法
について説明する。In the composite plating method according to the present invention, a method for manufacturing a plating solution will be explained.
■ ナフトール誘導体１〜５ｇ／ｌを含む水溶液中に無
機物粒子を添加し、充分に攪拌して無機物粒子表面をナ
フトール誘導体によりコーティングする。(2) Inorganic particles are added to an aqueous solution containing 1 to 5 g/l of a naphthol derivative and thoroughly stirred to coat the surface of the inorganic particles with the naphthol derivative.
■ ■の浴にシランカップリング剤を０．１〜０ 、３
ｖｔ％添加して充分に攪拌を行ない、加水分解したシ
ランカップリング剤を無機物粒子表面に固定化させる。■ Add 0.1 to 0.3 silane coupling agent to the bath of ■.
vt% is added and sufficiently stirred to immobilize the hydrolyzed silane coupling agent on the surface of the inorganic particles.
■ ■の浴を他の容器のめっき浴中に少しずつ攪拌しな
がら添加し、充分に攪拌してめっき浴中のＦｅ”、Ｎｌ
”、Ｃｏ” 、Ｍｎ”＋吸着により無機物粒子を正に帯
電させる（合金浴のばあい）。■ Add the bath of ■ to the plating bath in another container little by little while stirring, and stir thoroughly to remove the
Inorganic particles are positively charged by ", Co", Mn"+ adsorption (in the case of an alloy bath).
このようにして製造しためっき浴で電解処理することに
より、亜鉛または亜鉛系合金マトリックス中にシランカ
ップリング剤と化学結合した無機物粒子を均一に分散さ
せた複合めっき鋼板が得られる。このめっき皮膜中の無
機物粒子に固定化したシランカップリング剤はアミノ基
またはエポキシ基を含む有機官能基をめっき表面に固定
化するので疎水性となり、耐蝕性と塗装性を向上させる
のである。By electrolytically treating in the plating bath produced in this way, a composite plated steel sheet can be obtained in which inorganic particles chemically bonded to a silane coupling agent are uniformly dispersed in a zinc or zinc-based alloy matrix. The silane coupling agent immobilized on the inorganic particles in the plating film immobilizes organic functional groups including amino groups or epoxy groups on the plating surface, making it hydrophobic and improving corrosion resistance and paintability.
本発明に係る複合めっき法において使用４−るめっき浴
中の金属イオン濃度は、Ｚｎ”が２０〜９０ｇ／ｌ、Ｆ
ｅ” 、Ｎｉ” Ｎ Ｃｏ” 、Ｍｎ”＋は１種または
２種以上の混合物で５〜６０ｇ／ｌとするのがよい。ま
た、無機物粒子濃度は５〜１５０ｇ／ｌとすることによ
り良好な結果が得られ、５ｇ／１未満では無機物の共析
率が少なすぎ、１５０ｇ／ｌを越えるとマトリックスと
なる亜鉛、亜鉛系合金の析出が抑制され、密着性が劣化
する。The metal ion concentration in the 4-ru plating bath used in the composite plating method according to the present invention is 20 to 90 g/l of Zn'', F
e", Ni"N Co", and Mn"+ are preferably used alone or as a mixture of two or more in an amount of 5 to 60 g/l. In addition, good results can be obtained by setting the inorganic particle concentration to 5 to 150 g/l; if it is less than 5 g/l, the eutectoid rate of inorganic particles is too small; if it exceeds 150 g/l, zinc or zinc-based alloys that form the matrix precipitation is suppressed and adhesion deteriorates.
また、複合めっき皮膜組成は、亜鉛系合金の場合、Ｆｅ
５Ｎｔ、Ｃｏ、Ｍｎが総量で１〜３０ｗｔ％とするのが
よく、１ｗｔ％未満では合金化による耐蝕性向上が不充
分であり、また、３０ｗｔ％を越えると耐蝕性が劣化す
る。In addition, the composition of the composite plating film is Fe
The total amount of 5Nt, Co, and Mn is preferably 1 to 30 wt%; if it is less than 1 wt%, the improvement in corrosion resistance by alloying is insufficient, and if it exceeds 30 wt%, the corrosion resistance deteriorates.
さらに、無機物粒子の共析率は０．５〜１０ｗｔ％とす
るのがよく、０ 、５ ｗｔ％未満では耐蝕性および塗
装性の向上が不充分であり、また、１″Ｏｗｔ％を越え
ると密着性が劣化する。Furthermore, the eutectoid ratio of inorganic particles is preferably 0.5 to 10 wt%; if it is less than 0.5 wt%, the improvement in corrosion resistance and paintability is insufficient, and if it exceeds 1" Owt%, Adhesion deteriorates.
そして、電着量はめっき密む性、加工性の問題から、２
〜１００ ｇ／ｎ＋”が望ましく、２ｇ／ｍ”未満では
薄すぎて耐蝕性の向上効果が少なく、また、１００ ｇ
／ｍ”を越えるとめっきの密着性および加工性が悪くな
る。The amount of electrodeposition was determined by the problem of plating density and processability.
~100 g/n+" is desirable; less than 2 g/m" is too thin and has little effect on improving corrosion resistance;
/m'', plating adhesion and workability deteriorate.
めっき浴の温度は４０〜６０℃、叶■は１〜４とするの
がよく、ｐｕｔ未満では無機物の共析率が少なすぎ、ｐ
Ｈ４を越えると無機物はめっき表面に網目状態に析出し
、耐蝕性、密着性が悪くなり、また、浴の攪拌は無機物
粒子か共析し易い範囲があり、目的とする組成とするた
めには一定の攪拌を行なうのがよい。The temperature of the plating bath should be 40 to 60℃, and the temperature should be 1 to 4. If it is less than put, the eutectoid rate of inorganic matter will be too small, and p
If H4 is exceeded, inorganic substances will precipitate in a network on the plating surface, resulting in poor corrosion resistance and adhesion.Additionally, there is a range in which inorganic particles are likely to eutectoid when stirring the bath, so in order to obtain the desired composition, It is advisable to carry out constant stirring.
電流密度は、浴の攪拌により決定されるが、５〜８０Ａ
／ｄｌｓの範囲カヨク、５Ａ／ｄｌｉ！未満テハ共折率
が少なずぎ、また、８０ Ａ／ｄ＋ｓ″を越えるとめっ
き金属が焼き付いた粗めっきとなる。The current density is determined by stirring the bath, but is between 5 and 80 A.
/dls range Kayoku, 5A/dli! If the co-refraction index is too small, and if it exceeds 80 A/d+s'', the plated metal will be baked into rough plating.
耐蝕性は塩水噴霧試験（ＪＩＳ Ｚ ２３７１）により
評価した。また、上塗塗料密着性は市販のミラミンアル
キート塗料を２０μｍスプレー塗布し、１２０℃の温度
で２０分焼き付け、折り曲げて評価した。Corrosion resistance was evaluated by a salt spray test (JIS Z 2371). The adhesion of the top coat was evaluated by spraying 20 μm of commercially available Miramine Alkyte paint, baking at 120° C. for 20 minutes, and bending.
［実 施 例］ 本発明に係る複合めっき法の実施例を説明する。[Example] An example of the composite plating method according to the present invention will be described.
実施例！
平均粒径０．０２μｍの５ｉＯｖ粒子を、ナフトール誘
導体（非イオン界面活性剤）４ｇ／ｌを含む水溶液に添
加し、充分に攪拌した後、γ−グリシドキシプロピルメ
チルジェトキシシランを２ｗｔ％となるように添加、攪
拌して５ｉＯｚ表面に固定化させろ。 このように処理
されたＳｉｎ、ゾル（５度２００ｇ／ｌ）をめっき浴に
加え、電気めっき処理を行なった。Example! 5 iOv particles with an average particle size of 0.02 μm were added to an aqueous solution containing 4 g/l of a naphthol derivative (nonionic surfactant), and after thorough stirring, γ-glycidoxypropylmethyljethoxysilane was added to 2 wt%. Add and stir until it is immobilized on the 5iOz surface. The thus treated Sin and sol (5 degrees, 200 g/l) were added to a plating bath, and electroplating was performed.
めっき浴組成
ＺｎＳＯ４７ＨｔＯ： ２００ｇ／ｌＦｅ５０＊”７
ＨｔＯ： ３００ｇ／１（ＮＨ，）ｔｓｏ、
： ３０ ｇ／ｌ５ｉＯ＊
： ５ ｏｇ／ｌ電解条件
電流密度 ； ４０Δ／ｄｉ”ｐＨ２
浴温 ： ６０℃
攪拌 ２ｍ／ｓ
付着量 ： ２０ｇ／が比較材！は、
シランカップリング剤処理をしないものであり、比較材
１′はＳ ｉ Ｏを粒子を含まない合金めっき鋼板であ
る。Plating bath composition ZnSO47HtO: 200g/lFe50*”7
HtO: 300g/1(NH,)tso,
: 30 g/l5iO*
: 5 og/l Electrolytic condition current density; 40Δ/di”pH2 Bath temperature: 60°C Stirring 2m/s Coating amount: 20g/ is the comparison material!
Comparative material 1' was not treated with a silane coupling agent, and was an alloy plated steel sheet containing no SiO particles.
本発明に係る複合めっき法により製造されたＺローＦＦ
ｅ−５ｔｏ複合めっきｗ４板は、第１表に示すように良
好な耐蝕性および塗装性を示していることは明らかであ
る。Z-low FF manufactured by the composite plating method according to the present invention
It is clear that the e-5to composite plated W4 plate exhibits good corrosion resistance and paintability as shown in Table 1.
実施例２
実施例１の８１０１粒子の代わりに、平均粒径０．０２
μｌのＴｉｅ、粒子を用いて電気めっきを行なった。Example 2 Instead of the 8101 particles of Example 1, the average particle size was 0.02
Electroplating was performed using μl of Tie particles.
比較材２はシランカップリング剤による処理を行なわな
いものである。Comparative material 2 was not treated with a silane coupling agent.
本発明に係る複合めっき法により製造されたＺｎ −Ｆ
ｅ −Ｔ ｔｏ を複合めっき鋼板は第１表に示すよう
に良好な耐蝕性と塗装性を示している。Zn-F manufactured by the composite plating method according to the present invention
As shown in Table 1, the e-T to composite plated steel sheet exhibits good corrosion resistance and paintability.
実施例３
平均粒径０．０２μｍの５ｉｄｅ粒子をナフトール誘導
体（非イオン界面活性剤）の４ｇ／ｌを含む水溶液中に
両力１比、充分に攪拌した後、γ−グリシドキシプロピ
ルメチルジェトキシシランを２ｗｔ％となるように添加
、攪拌してＳｔｏｗ表面に固定化させる。Example 3 After thoroughly stirring 5ide particles with an average particle size of 0.02 μm in an aqueous solution containing 4 g/l of a naphthol derivative (nonionic surfactant) at a ratio of 1 to 1, γ-glycidoxypropyl methyl gel was added. Toxysilane is added to a concentration of 2 wt % and stirred to be immobilized on the surface of the Stow.
こうして得られたＳｉｎ、ゾル（濃度２００ｇ／ｍ）を
めっき浴に加え電気めっきを行なった。The thus obtained Sin sol (concentration 200 g/m) was added to a plating bath to perform electroplating.
めっき浴組成
ＺｎＳＯ４・７ＨｔＯ： ２００ｇ／ｌＮｉＳＯ４・
６Ｈ，Ｏ： ３００ｇ／１（ＮＨ，）ｔ・Ｓ ０４
： ３０ ｇ／ ＩＳ ｉＯｚ
： ５０ｇ／ １電解条件
実施例１と同じ
比較材３はシランカップリング剤による処理を行なわな
いものである。比較材３′は５ｉＯｚを含まないもので
ある。Plating bath composition ZnSO4・7HtO: 200g/lNiSO4・
6H,O: 300g/1(NH,)t・S 04
: 30g/IS iOz
: 50 g/1 Electrolytic conditions Comparative material 3, which is the same as Example 1, was not treated with a silane coupling agent. Comparative material 3' does not contain 5iOz.
本発明に係る複合めっき法により製造されたＺｎ−Ｎｉ
−５ｉＯｚ複合めっき鋼板は第１表に示すように良好な
耐蝕性および塗装性を示している。Zn-Ni manufactured by the composite plating method according to the present invention
As shown in Table 1, the -5iOz composite plated steel sheet exhibits good corrosion resistance and paintability.
実施例４
実施例３の９１０ｗ粒子の代わりに、平均粒径０．０２
μｍまＺｒｏｔ粒子を用い、また、シランカップリング
剤としてＮ−β（アミノエチル）γ−アミノプロピルメ
チルジメトキシシランを用いて処理を行ない、電気めっ
きを行なった。Example 4 Instead of the 910w particles of Example 3, an average particle size of 0.02
Electroplating was performed using μm Zrot particles and N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane as a silane coupling agent.
比較材４はシランカップリング剤による処理を行なわな
いものである。Comparative material 4 was not treated with a silane coupling agent.
本発明に係る複合めっき法により製造されたＺｎ Ｎ
ｉ ’Ｚ、ｒｏｔ複合めっき鋼板は、第１表に示すよ
うに良好な耐蝕性および塗装性を示している。ZnN produced by the composite plating method according to the present invention
The i'Z, rot composite plated steel sheet exhibits good corrosion resistance and paintability as shown in Table 1.
［発明の効果］
以上説明したように、本発明に係る複合めっき法は上記
の構成を有しているものであるから、製造された複合め
っき鋼板は、優れた耐蝕性および塗装性を有しているも
のである。[Effects of the Invention] As explained above, since the composite plating method according to the present invention has the above configuration, the manufactured composite plated steel sheet has excellent corrosion resistance and paintability. It is something that
Claims (2)
ＺｒＯ＿２、Ｔａ＿２Ｏ＿５の１種または２種以上を非
イオン界面活性剤およびシランカップリング剤を含む液
中で処理後、亜鉛或いは亜鉛とニッケル、鉄、コバルト
、マンガンの１種または２種以上の合金めっき液中に添
加し、電解処理することを特徴とする複合めっき法。(1) SiO_2, TiO_2 with a particle size of 0.1 μm or less,
After processing one or more of ZrO_2 and Ta_2O_5 in a solution containing a nonionic surfactant and a silane coupling agent, plating with zinc or one or more alloys of zinc and nickel, iron, cobalt, and manganese. A composite plating method characterized by adding it to a liquid and electrolytically treating it.
、シランカップリング剤は無機物と化学結合する反応基
がメトキシ基或いはエトキシ基で、有機物と化学結合す
る反応基がアミノ基またはエポキシ基を含むものである
ことを特徴とする特許請求の範囲第１項記載の複合めっ
き法。(2) The nonionic surfactant is a naphthol derivative, the silane coupling agent has a reactive group that chemically bonds with an inorganic substance is a methoxy group or an ethoxy group, and a reactive group that chemically bonds with an organic substance contains an amino group or an epoxy group. A composite plating method according to claim 1, characterized in that the method comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11398087A JPS63277797A (en) | 1987-05-11 | 1987-05-11 | Composite plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11398087A JPS63277797A (en) | 1987-05-11 | 1987-05-11 | Composite plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63277797A true JPS63277797A (en) | 1988-11-15 |
Family
ID=14626038
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11398087A Pending JPS63277797A (en) | 1987-05-11 | 1987-05-11 | Composite plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63277797A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262528A (en) * | 2006-03-29 | 2007-10-11 | Kumamoto Univ | Method of manufacturing composite plated material |
| JP2011528063A (en) * | 2008-07-15 | 2011-11-10 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for electrodepositing metal on a substrate |
| JP2018044221A (en) * | 2016-09-16 | 2018-03-22 | 本田技研工業株式会社 | Zinc-nickel composite plating bath, zinc-nickel composite plating film, die and plating method |
-
1987
- 1987-05-11 JP JP11398087A patent/JPS63277797A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007262528A (en) * | 2006-03-29 | 2007-10-11 | Kumamoto Univ | Method of manufacturing composite plated material |
| JP2011528063A (en) * | 2008-07-15 | 2011-11-10 | アトーテヒ ドイッチュラント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Method for electrodepositing metal on a substrate |
| JP2018044221A (en) * | 2016-09-16 | 2018-03-22 | 本田技研工業株式会社 | Zinc-nickel composite plating bath, zinc-nickel composite plating film, die and plating method |
| WO2018052023A1 (en) * | 2016-09-16 | 2018-03-22 | 本田技研工業株式会社 | Zinc-nickel composite plating bath, zinc-nickel composite plating film, mold and plating method |
| US11078586B2 (en) | 2016-09-16 | 2021-08-03 | Honda Motor Co., Ltd. | Zinc-nickel composite plating bath, zinc-nickel composite plating film, mold and plating method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0323756B1 (en) | Corrosion-resistant plated composite steel strip and method of producing same | |
| CA1063966A (en) | Electroplating method | |
| AU604526B2 (en) | Zn-based composite-plated metallic material and plating method | |
| US4086153A (en) | Method of producing a composite coated steel sheet | |
| JPS626760B2 (en) | ||
| KR910002956B1 (en) | Composite zinc-silica electro-galvanized steel sheet excellent in corrosion resistance | |
| EP0291606B1 (en) | High corrosion resistant plated composite steel strip and method for producing same | |
| JPS63277797A (en) | Composite plating method | |
| JP2690629B2 (en) | Organic composite coated steel sheet with excellent corrosion resistance and spot weldability | |
| JPH0359152B2 (en) | ||
| CA1116548A (en) | Method of producing a composite coated steel sheet | |
| JPH01246398A (en) | Production of composite dispersive particles and composite plating method | |
| JPS59123796A (en) | Production of electrogalvanized steel sheet having high corrosion resistance | |
| JPH0368793A (en) | Surface-treated material having superior chemical convertibility and production thereof | |
| JPH05331693A (en) | Electroplated steel seet and its manufacture | |
| JPS60177187A (en) | Fe-p plated steel sheet with superior suitability to phosphating | |
| JPH042677B2 (en) | ||
| JP2733865B2 (en) | Method for producing Cr-containing zinc alloy-based organic dispersion coated steel sheet having excellent corrosion resistance and workability | |
| JPH01230797A (en) | Zn-ni composite electroplated steel sheet having superior corrosion resistance and workability | |
| JPS61113787A (en) | Cold rolled steel sheet having excellent phosphating property | |
| CA2036464A1 (en) | Method for manufacturing zinc-silica composite electroplated steel sheet | |
| JPH0211799A (en) | Zn-based surface-treated steel sheet having excellent corrosion resistance after coating | |
| JPH01279798A (en) | Composite electroplated steel sheet having high corrosion resistance | |
| JPS63105979A (en) | Highly corrosion resistant multilayer plated steel sheet | |
| JPH02159398A (en) | Production of composite plated steel sheet having high corrosion resistance |