JP6839839B2 - Black chrome plating method - Google Patents
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- JP6839839B2 JP6839839B2 JP2017004045A JP2017004045A JP6839839B2 JP 6839839 B2 JP6839839 B2 JP 6839839B2 JP 2017004045 A JP2017004045 A JP 2017004045A JP 2017004045 A JP2017004045 A JP 2017004045A JP 6839839 B2 JP6839839 B2 JP 6839839B2
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- 238000007747 plating Methods 0.000 title claims description 99
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 53
- 238000000034 method Methods 0.000 title claims description 33
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- -1 magnesium fluorinated magnesium Chemical class 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000004744 fabric Substances 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 4
- 241000269821 Scombridae Species 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000020640 mackerel Nutrition 0.000 description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 3
- 239000000391 magnesium silicate Substances 0.000 description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 description 3
- 235000019792 magnesium silicate Nutrition 0.000 description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003109 potassium Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
本発明は黒色クロムメッキ方法に関する。 The present invention relates to a black chrome plating method.
メッキ浴の無水クロム酸に、弗化化合物、バリウム化合物、二酸化マンガン等を添加する黒色クロムメッキ方法は開発されている。（特許文献１、２参照） A black chrome plating method has been developed in which a fluoride compound, a barium compound, manganese dioxide, or the like is added to chromic anhydride in a plating bath. (See Patent Documents 1 and 2)
特許文献１のメッキ方法は、旧来の黒色クロムメッキ方法の欠点であった、メッキ浴を１０℃以下の低温に冷却し、さらに、電流密度を５０Ａ／ｄｍ２以上とする厳しいメッキ条件を改善するために、無水クロム酸に加えて、水溶性不飽和脂肪族アルコールや水溶性芳香族アルコールをメッキ浴に添加する。この黒色クロムメッキ方法は、メッキ浴に、水溶性不飽和脂肪族アルコール等を添加することで、電流密度を低く、メッキ浴の温度を常温として黒色クロムメッキを実現する。さらに、この公報は、メッキ浴に、弗化化合物として、弗化水素酸、弗化ソーダ、弗化カリウム、弗化アンモン、弗化マグネシウム、珪弗酸、珪弗化ソーダ、珪弗化カリ、珪弗化アンモン、硼弗酸、硼弗化ソーダ、硼弗カリ、硼弗化アンモンなどを使用することも記載する。 The plating method of Patent Document 1 improves the strict plating conditions of cooling the plating bath to a low temperature of 10 ° C. or lower and further setting the current density to 50 A / dm 2 or more, which is a drawback of the conventional black chrome plating method. Therefore, in addition to chromic anhydride, a water-soluble unsaturated fatty alcohol or a water-soluble aromatic alcohol is added to the plating bath. In this black chrome plating method, black chrome plating is realized by adding a water-soluble unsaturated fatty alcohol or the like to the plating bath to reduce the current density and keep the temperature of the plating bath at room temperature. Furthermore, in this publication, hydrofluoric acid, sodium fluoride, potassium fluoride, ammon fluoride, magnesium fluoride, silicic acid, sodium silicylated, potassium silica fluoride, as a fluoride compound, are added to the plating bath. It is also described that silicofluorinated ammon, borofluoric acid, borofluorinated soda, borofluorinated potassium, borofluorinated ammon and the like are used.
また、特許文献２のメッキ方法は、メッキ浴に無水クロム酸に加えて二酸化マンガンを添加し、無水クロム酸と二酸化マンガンの添加濃度の組み合わせを調整して、灰色、灰黒色、真黒色、青黒色などの任意の色調のクロムメッキ膜を実現する。この黒色クロムメッキ方法も、メッキ浴の温度と電流密度を広い範囲でメッキする特徴も実現する。 Further, in the plating method of Patent Document 2, manganese dioxide is added to the plating bath in addition to chromic anhydride, and the combination of the addition concentrations of chromic anhydride and manganese dioxide is adjusted to make gray, grayish black, pure black, and blue. Achieves a chrome-plated film of any color such as black. This black chrome plating method also realizes the feature of plating the temperature and current density of the plating bath in a wide range.
以上の黒色クロムメッキ方法は、厳しいメッキ条件、すなわち高い電流密度と、低温に冷却するメッキ浴の温度条件とを解消して、メッキ処理をコストダウンできる。また、これ等の黒色クロムメッキ方法は、旧来の黒色クロムメッキに比較すると優れた耐食性を実現するが、さらに厳しい環境に使用されて必ずしも満足できる耐食性を実現できない。とくに、黒色クロムメッキは、メッキ膜に微細なクラックが発生し、このクラックが厳しい使用環境における優れた耐食性の実現を難しくする。さらに、微細なクラックは黒色クロムメッキ膜の密着性を低下させる原因ともなって、使用環境によっては剥離しやすい欠点がある。 The above black chrome plating method can eliminate severe plating conditions, that is, high current density and temperature conditions of a plating bath cooled to a low temperature, and can reduce the cost of the plating process. Further, these black chrome plating methods realize excellent corrosion resistance as compared with the conventional black chrome plating, but they cannot always realize satisfactory corrosion resistance when used in a harsher environment. In particular, black chrome plating causes fine cracks in the plating film, which makes it difficult to realize excellent corrosion resistance in a harsh usage environment. Further, the fine cracks cause a decrease in the adhesion of the black chrome plating film, and have a drawback that they are easily peeled off depending on the usage environment.
本発明は、さらに弊害を解消することを目的に開発されたもので、本発明の重要な目的は、極めて厳しい使用環境においても優れた耐食性と密着性とを実現する黒色クロムメッキ方法を提供することにある。 The present invention has been developed for the purpose of further eliminating adverse effects, and an important object of the present invention is to provide a black chrome plating method that realizes excellent corrosion resistance and adhesion even in an extremely harsh usage environment. There is.
本発明の黒色クロムメッキ方法は、３５０ｇ／リットルないし４５０ｇ／リットルの無水クロム酸と、５ｇ／リットルないし１３ｇ／リットルの炭酸バリウムに加えて、０．１ｇ／リットルないし０．２ｇ／リットルのケイ弗化マグネシウムと、６ｍリットル／リットルないし１２ｍリットル／リットルのリン酸とを添加してメッキ浴とし、電流密度を２５Ａ／ｄｍ２ないし３５Ａ／ｄｍ２、溶液温度を１５℃ないし２５℃、メッキ時間を５分ないし２０分として黒色クロムメッキ膜を設ける。 The black chrome plating method of the present invention comprises 350 g / liter to 450 g / liter of chromium anhydride and 5 g / liter to 13 g / liter of barium carbonate, plus 0.1 g / liter to 0.2 g / liter of silicate. Magnesium oxide and 6 ml / liter to 12 ml / liter of phosphoric acid are added to make a plating bath, the current density is 25 A / dm 2 to 35 A / dm 2 , the solution temperature is 15 ° C to 25 ° C, and the plating time is set. A black chrome plating film is provided for 5 to 20 minutes.
以上の黒色クロムメッキ方法は、無水クロム酸と炭酸バリウムに加えて、メッキ浴には特定量のケイ弗化マグネシウムと硝酸ナトリウムとリン酸とを添加することで、従来のいかなる黒色クロムメッキ膜によっても実現できなかった、優れた耐食性と密着性とを実現する。黒色クロムメッキ膜の優れた耐食性と密着性は、特定組成のメッキ浴によって、微細なクラックの発生が著しく改善され、微細なクラックからの浸水に起因する耐食性と密着性を阻止することで実現される。ちなみに、本発明の実施例によって得られた黒色クロムメッキ膜は、６７２時間の耐食試験において全く発鯖が認められない。 In the above black chrome plating method, in addition to chromic anhydride and barium carbonate, a specific amount of magnesium silica fluoride, sodium nitrate and phosphoric acid are added to the plating bath, so that any conventional black chrome plating film can be used. Achieves excellent corrosion resistance and adhesion, which could not be achieved. The excellent corrosion resistance and adhesion of the black chrome plating film is realized by significantly improving the occurrence of fine cracks by the plating bath of a specific composition and preventing the corrosion resistance and adhesion caused by the infiltration of water from the fine cracks. To. Incidentally, in the black chrome-plated film obtained by the examples of the present invention, no mackerel was observed in the corrosion resistance test for 672 hours.
５ｗｔ％の塩水を直接に噴霧する塩水の加速試験においても、１２０時間後におけるレイティングナンバーが９．８（鯖発生率０．０２％以下）、１５０時間後におけるレイティングナンバーが９．７とほとんど変化せず、極めて優れた数値を示す（図１）。これに対して、ケイ弗化マグネシウムとリン酸を添加しないメッキ浴でメッキされた黒色クロムメッキ膜は、１２０時間後におけるレイティングナンバーが５と実施例に比較して著しく低下した（図２）。 Even in the accelerated test of salt water in which 5 wt% salt water is directly sprayed, the rating number after 120 hours is 9.8 (mackerel occurrence rate 0.02% or less), and the rating number after 150 hours is 9.7, which is almost the same. However, it shows extremely excellent numerical values (Fig. 1). On the other hand, the black chrome plating film plated in the plating bath to which magnesium silicescent fluoride and phosphoric acid were not added had a rating number of 5 after 120 hours, which was significantly lower than that of the examples (FIG. 2).
耐食試験は温度／湿度を４９℃／９５％として、２４時間、４８時間、７２時間、９６時間、１６８時間、３３６時間、５０４時間、６７２時間後における鯖の発生状態を検査し、
塩水の加速度試験は、３５℃の温度環境において、５ｗｔ％の塩水を試験片に直接に噴霧して、試験片の表面に塩水が付着する状態として、１２０時間後おける表面の錆の状態を検査した。
In the corrosion resistance test, the temperature / humidity was set to 49 ° C./95%, and the state of mackerel generation after 24 hours, 48 hours, 72 hours, 96 hours, 168 hours, 336 hours, 504 hours, and 672 hours was inspected.
In the salt water acceleration test, 5 wt% salt water is sprayed directly onto the test piece in a temperature environment of 35 ° C., and the state of rust on the surface after 120 hours is inspected as the state where the salt water adheres to the surface of the test piece. did.
密着性の試験は、黒色クロムメッキ膜の表面に、粘着層のある布テープを貼り付けて１０秒間強く押圧し、その後、布テープを瞬間的に引き剥がして、布テープの表面にメッキ膜が付着する状態を目視で観察し、さらに布テープが引き剥がされた金属プレート表面におけるメッキ膜の剥離と膨れを目視した。 In the adhesion test, a cloth tape with an adhesive layer is attached to the surface of the black chrome plating film and pressed strongly for 10 seconds, and then the cloth tape is momentarily peeled off to form a plating film on the surface of the cloth tape. The state of adhesion was visually observed, and further, the peeling and swelling of the plating film on the surface of the metal plate from which the cloth tape was peeled off was visually observed.
本発明の黒色クロムメッキ方法は、この密着性の試験において、引き剥がした布テープ表面にメッキ膜が付着せず、ます、布テープの引き剥がし部分においてメッキ膜の剥離も膨れも全く発生しなかった。ケイ弗化マグネシウムとリン酸を添加しない従来のメッキ浴でメッキされたメッキ膜は、密着性の試験において、一部が布テープの表面に付着し、また、引き剥がされた部分には、一部にメッキ膜の剥離が発生した。 In this adhesion test, the black chrome plating method of the present invention does not cause the plating film to adhere to the surface of the peeled cloth tape, and neither peeling nor swelling of the plating film occurs at the peeled portion of the cloth tape. It was. In the adhesion test, a part of the plating film plated in the conventional plating bath without adding magnesium silica fluoride and phosphoric acid adhered to the surface of the cloth tape, and the part that was peeled off was one. Peeling of the plating film occurred on the part.
本発明の黒色クロムメッキ方法は、メッキ浴に、１０ｇ／リットルないし２０ｇ／リットルの蓚酸と、１ｇ／リットルないし５ｇ／リットルの３価クロムを添加することができ、このメッキ浴はさらに優れた耐食性と密着性とを実現する。 In the black chrome plating method of the present invention, 10 g / liter to 20 g / liter of oxalic acid and 1 g / liter to 5 g / liter of trivalent chromium can be added to the plating bath, and this plating bath has even better corrosion resistance. And adhesion.
さらにまた、本発明の黒色クロムメッキ方法は、無水クロム酸の添加量を３６０ｇ／リットルないし４２０ｇ／リットルと、炭酸バリウムの添加量を８ｇ／リットルないし１０ｇ／リットルとし、ケイ弗化マグネシウムの添加量を０．１５ｇ／リットルないし０．１７ｇ／リットルとすることができる。また、メッキ時間を８分ないし１５分とすることもできる。 Furthermore, in the black chrome plating method of the present invention, the amount of chromic anhydride added is 360 g / liter to 420 g / liter, the amount of barium carbonate added is 8 g / liter to 10 g / liter, and the amount of magnesium silicate added. Can be 0.15 g / liter to 0.17 g / liter. Further, the plating time can be set to 8 to 15 minutes.
以下、本発明の実施例を図面に基づいて説明する。ただし、以下に示す実施例は、本発明の技術思想を具体化するための黒色クロムメッキ方法を例示するものであって、本発明は黒色クロムメッキ方法を以下の方法に特定しない。さらに、この明細書は、特許請求の範囲に示される部材を、実施例の部材に特定するものでは決してない。 Hereinafter, examples of the present invention will be described with reference to the drawings. However, the examples shown below exemplify a black chrome plating method for embodying the technical idea of the present invention, and the present invention does not specify the black chrome plating method as the following method. Furthermore, this specification never specifies the members shown in the claims as the members of the examples.
本発明のクロムメッキ方法は、導電性プレートを前処理した後、その表面にクロムメッキ膜を生成する。前処理工程は、導電性プレートの表面に付着する油成分を脱脂液に浸漬して除去した後、水洗して脱脂液を除去し、その後、さらに水洗した後、一般的な活性化処理、水洗して処理される。 In the chrome plating method of the present invention, a chrome plating film is formed on the surface of the conductive plate after pretreatment. In the pretreatment step, the oil component adhering to the surface of the conductive plate is removed by immersing it in a degreasing solution, then washed with water to remove the degreasing solution, and then further washed with water, followed by general activation treatment and washing with water. Is processed.
導電性プレートは、鉄、亜鉛、銅、アルミニウム、ステンレス等、金属やこれ等の金属合金からなる金属板、無電解メッキにより導電化処理された各種のセラミックスやプラスチックス等が使用できる。 As the conductive plate, a metal plate made of metal or a metal alloy such as iron, zinc, copper, aluminum, stainless steel, etc., various ceramics and plastics conductively treated by electroless plating can be used.
さらに、導電性プレートは、黒色クロムメッキ膜の下地層を設けて、下地層の上に黒色クロムメッキ膜を設けることもできる。下地層にはニッケルメッキ層等が使用できる。 Further, the conductive plate may be provided with a base layer of a black chrome plating film, and a black chrome plating film may be provided on the base layer. A nickel-plated layer or the like can be used as the base layer.
導電性プレートを電気メッキする黒色クロムメッキ方法は、メッキ浴は、無水クロム酸と炭酸バリウムに加えて、ケイ弗化マグネシウムとリン酸とを添加する。
メッキ浴は、無水クロム酸の添加量を、３５０ｇ／リットルないし４５０ｇ／リットルとする。無水クロム酸の添加量は、少なすぎると黒色クロムメッキ膜の色相が灰色となる傾向が強くなり、多すぎると電着性が低下することに加え、綺麗な真黒ないし青黒色のメッキ膜にできないので、より好ましくは、３６０ｇ／リットルないし４２０ｇ／リットルとする。
In the black chrome plating method of electroplating a conductive plate, in the plating bath, magnesium silicate and phosphoric acid are added in addition to chromic anhydride and barium carbonate.
In the plating bath, the amount of chromic anhydride added is 350 g / liter to 450 g / liter. If the amount of chromic anhydride added is too small, the hue of the black chrome plating film tends to be gray, and if it is too large, the electrodeposition property is lowered and a beautiful black or blue-black plating film cannot be obtained. Therefore, it is more preferably 360 g / liter to 420 g / liter.
炭酸バリウムの添加量は、５ｇ／リットルないし１３ｇ／リットルとする。炭酸バリウムの添加量が少なすぎると、残存する硫酸根によって好ましい黒色のクロムメッキ膜を生成できなくなり、反対に多すぎると黒色クロムメッキ膜の安定性が低下するので、より好ましくは、８ｇ／リットルないし１０ｇ／リットルとしてメッキ浴の硫酸根を減少させる。 The amount of barium carbonate added is 5 g / liter to 13 g / liter. If the amount of barium carbonate added is too small, the residual sulfate roots cannot form a preferable black chrome-plated film, and if it is too large, the stability of the black chrome-plated film decreases. Reduce the sulfate roots in the plating bath to or 10 g / liter.
ケイ弗化マグネシウムの添加量は、０．１ｇ／リットルないし０．２ｇ／リットル、好ましくは０．１５ｇ／リットルないし０．１７ｇ／リットルと極めて限られた範囲に特定される。ケイ弗化マグネシウムの添加量は、以上の範囲よりも多すぎても、また少なすぎても、好ましい黒色ないし青黒色のクロムメッキ膜を実現できない。したがって、ケイ弗化マグネシウムの添加量は、金属プレート表面に電着される黒色クロムメッキ膜の色相を考慮し、また用途に要求される色相を考慮して、以上の範囲で用途や金属プレートの形状を考慮して最適値に調整される。 The amount of magnesium silica fluoride added is specified in a very limited range of 0.1 g / liter to 0.2 g / liter, preferably 0.15 g / liter to 0.17 g / liter. If the amount of magnesium silica fluoride added is too much or too little than the above range, a preferable black to blue-black chrome-plated film cannot be realized. Therefore, the amount of magnesium silica fluoride added is within the above range in consideration of the hue of the black chrome plating film electrodeposited on the surface of the metal plate and the hue required for the application. It is adjusted to the optimum value in consideration of the shape.
メッキ浴は、無水クロム酸と炭酸バリウムに加えて、ケイ弗化マグネシウムと硝酸ナトリウムとリン酸が添加されて、好ましい真黒ないし青黒色とし、さらに、微細なクラックの発生を防止して安定に黒色クロムメッキ膜を生成する。メッキ浴に添加される硝酸ナトリウムの添加量は、２ｇ／リットルないし５ｇ／リットル、好ましくは３．５ｇ／リットルないし４．０ｇ／リットルと極めて制限された範囲に特定する。 In the plating bath, in addition to chromic anhydride and barium carbonate, magnesium silicate, sodium nitrate and phosphoric acid are added to make a preferable pure black to bluish black, and further, the occurrence of fine cracks is prevented and the plating bath is stably black. Produces a chrome-plated film. The amount of sodium nitrate added to the plating bath is specified in a very limited range of 2 g / liter to 5 g / liter, preferably 3.5 g / liter to 4.0 g / liter.
さらに、メッキ浴は、１０ｇ／リットルないし２０ｇ／リットルの蓚酸と、１ｇ／リットルないし５ｇ／リットルの３価クロムを添加することで、より安定して黒色クロムメッキ膜を設けることができる。 Further, in the plating bath, a black chrome plating film can be provided more stably by adding 10 g / liter to 20 g / liter of oxalic acid and 1 g / liter to 5 g / liter of trivalent chromium.
電流密度は、好ましくは２５Ａ／ｄｍ２ないし３５Ａ／ｄｍ２とする。電流密度は小さすぎても大きすぎても好ましい真黒ないし青黒色のメッキ膜を実現できない。電流密度も、金属プレートの形状や用途に最適な真黒ないし青黒色とするように、以上の範囲で最適値に調整されるが、より好ましくは、２８Ａ／ｄｍ２ないし３２Ａ／ｄｍ２とする。金属プレートに凹部があると、凹部の電流密度が低下するので、金属プレートの形状を考慮し、黒色クロムメッキ膜の膜厚や真黒が最適な状態となるように電流密度を調整する。 The current density is preferably 25 A / dm 2 to 35 A / dm 2 . If the current density is too small or too large, a preferable black or blue-black plating film cannot be realized. The current density is also adjusted to the optimum value in the above range so as to be the optimum black to blue-black for the shape and application of the metal plate, but more preferably 28 A / dm 2 to 32 A / dm 2 . If the metal plate has recesses, the current density of the recesses decreases. Therefore, the current density is adjusted so that the film thickness and pure black of the black chrome plating film are optimized in consideration of the shape of the metal plate.
メッキ浴の温度は、１５℃ないし２５℃とすることができるので、加熱することなく、また冷却することなく常温としてランニングコストを低減できる。 Since the temperature of the plating bath can be 15 ° C. to 25 ° C., the running cost can be reduced at room temperature without heating or cooling.
黒色クロムメッキ膜の膜厚は、用途に最適な厚さに設定されるが、好ましくは１μｍ以上であって１０μｍ以下とする。 The film thickness of the black chrome plating film is set to an optimum thickness for the application, but is preferably 1 μm or more and 10 μm or less.
［実施例１］
導電性プレートとして、表面を梨地とする、図１に示す、平面状の金属板と円筒状の金属筒を使用し、これにリード線を接続して表面に膜厚を約３μｍとする黒色クロムメッキ膜を生成する。
以上の導電性プレートは、
無水クロム酸を３００ｇ／リットル、
炭酸バリウムを９ｇ／リットル、
ケイ弗化マグネシウムを０．１６ｇ／リットル、
硝酸ナトリウムを３．８ｇ／リットル、
リン酸を９ｍリットル／リットルとするメッキ浴を使用し、
メッキ浴の温度を２０℃、電流密度を３０Ａ／ｄｍ２とし、陽極としてグラファイト電極を用いて、１０分間メッキすると、導電性プレートの表面には、青黒色の綺麗な黒色クロムメッキ膜が生成された。
[Example 1]
As the conductive plate, a flat metal plate and a cylindrical metal cylinder shown in FIG. 1 having a satin finish on the surface are used, and a lead wire is connected to the flat metal plate and a black chrome having a film thickness of about 3 μm on the surface. Produces a plating film.
The above conductive plate
300 g / liter of chromic anhydride,
Barium carbonate 9g / liter,
Magnesium silica fluoride 0.16 g / liter,
3.8 g / liter of sodium nitrate,
Using a plating bath with phosphoric acid of 9 ml / liter,
When the plating bath temperature is 20 ° C., the current density is 30 A / dm 2, and plating is performed for 10 minutes using a graphite electrode as an anode, a beautiful blue-black chrome plating film is formed on the surface of the conductive plate. It was.
生成された黒色クロムメッキ膜は、５ｗｔ％の塩水を霧状にして直接に噴霧する塩水の加速試験においても１５０時間後にほとんど鯖が発生せず、４９℃、９５％の湿潤試験においては６７２時間後に発錆はなく、さらに布テープを貼り付ける密着性の試験においてもメッキ膜の剥離が全く無く、極めて優れた密着性を実現した。 The produced black chrome-plated film produced almost no rust after 150 hours even in the accelerated test of salt water in which 5 wt% salt water was atomized and directly sprayed, and 672 hours in the wet test at 49 ° C. and 95%. There was no rusting afterwards, and there was no peeling of the plating film in the adhesion test to which the cloth tape was attached, and extremely excellent adhesion was achieved.
本発明は、導電性プレートの表面に真黒ないし青黒色の黒色クロムメッキ膜を設けて耐食性と密着性が要求される用途に有効に利用できる。 INDUSTRIAL APPLICABILITY The present invention can be effectively used in applications where corrosion resistance and adhesion are required by providing a black chrome plating film of pure black to bluish black on the surface of a conductive plate.
Claims (6)
５ｇ／リットルないし１３ｇ／リットルの炭酸バリウムに加えて、
０．１ｇ／リットルないし０．２ｇ／リットルのケイ弗化マグネシウムと、
２ｇ／リットルないし５ｇ／リットルの硝酸ナトリウムと、
６ｍリットル／リットルないし１２ｍリットル／リットルのリン酸とを添加してメッキ浴とし、
電流密度を２５Ａ／ｄｍ２ないし３５Ａ／ｄｍ２、
溶液温度を１５℃ないし２５℃、
メッキ時間を５分ないし２０分として黒色クロムメッキ膜を設けることを特徴とする黒色クロムメッキ方法。 With 350 g / liter to 450 g / liter of chromic anhydride,
In addition to 5 g / liter to 13 g / liter barium carbonate,
With 0.1 g / liter to 0.2 g / liter of magnesium silica fluoride,
With 2 g / liter to 5 g / liter of sodium nitrate,
Add 6 ml / liter to 12 ml / liter of phosphoric acid to make a plating bath.
Current density is 25A / dm 2 to 35A / dm 2 ,
Solution temperature 15 ° C to 25 ° C,
A black chrome plating method characterized in that a black chrome plating film is provided with a plating time of 5 to 20 minutes.
前記メッキ浴に、１０ｇ／リットルないし２０ｇ／リットルの蓚酸と、１ｇ／リットルないし５ｇ／リットルの３価クロムを添加することを特徴とする黒色クロムメッキ方法。 The black chrome plating method according to claim 1.
A black chrome plating method comprising adding 10 g / liter to 20 g / liter of oxalic acid and 1 g / liter to 5 g / liter of trivalent chromium to the plating bath.
前記無水クロム酸の添加量を３６０ｇ／リットルないし４２０ｇ／リットルとすることを特徴とする黒色クロムメッキ方法。 The black chrome plating method according to claim 1.
A black chrome plating method characterized in that the amount of chromic anhydride added is 360 g / liter to 420 g / liter.
前記ケイ弗化マグネシウムの添加量を０．１５ｇ／リットルないし０．１７ｇ／リットルとすることを特徴とする黒色クロムメッキ方法。 The black chrome plating method according to any one of claims 1 to 4.
A black chrome plating method characterized in that the amount of magnesium fluorinated magnesium added is 0.15 g / liter to 0.17 g / liter.
メッキ時間を８分ないし１５分とすることを特徴とする黒色クロムメッキ方法。 The black chrome plating method according to any one of claims 1 to 5.
A black chrome plating method characterized in that the plating time is 8 to 15 minutes.
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