JP5517275B2 - Post-treatment agent for etching treatment with chromic acid-sulfuric acid mixture - Google Patents
Post-treatment agent for etching treatment with chromic acid-sulfuric acid mixture Download PDFInfo
- Publication number
- JP5517275B2 JP5517275B2 JP2006247671A JP2006247671A JP5517275B2 JP 5517275 B2 JP5517275 B2 JP 5517275B2 JP 2006247671 A JP2006247671 A JP 2006247671A JP 2006247671 A JP2006247671 A JP 2006247671A JP 5517275 B2 JP5517275 B2 JP 5517275B2
- Authority
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- Japan
- Prior art keywords
- resin molded
- molded product
- treatment
- plating
- solution
- 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.)
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- 238000005530 etching Methods 0.000 title claims description 44
- 239000003795 chemical substances by application Substances 0.000 title claims description 36
- KPVWDKBJLIDKEP-UHFFFAOYSA-L dihydroxy(dioxo)chromium;sulfuric acid Chemical compound OS(O)(=O)=O.O[Cr](O)(=O)=O KPVWDKBJLIDKEP-UHFFFAOYSA-L 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 title claims description 12
- 238000007747 plating Methods 0.000 claims description 79
- 239000000243 solution Substances 0.000 claims description 68
- 229920005989 resin Polymers 0.000 claims description 62
- 239000011347 resin Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 35
- 238000007772 electroless plating Methods 0.000 claims description 28
- 239000007864 aqueous solution Substances 0.000 claims description 24
- -1 aminopropyl group Chemical group 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- 238000009713 electroplating Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 150000002736 metal compounds Chemical class 0.000 claims description 9
- 239000005749 Copper compound Substances 0.000 claims description 8
- 150000001880 copper compounds Chemical class 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 4
- 125000006308 propyl amino group Chemical class 0.000 claims description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000010408 film Substances 0.000 description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 35
- 239000010949 copper Substances 0.000 description 35
- 229910052802 copper Inorganic materials 0.000 description 35
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 11
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 10
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 9
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 6
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 150000001720 carbohydrates Chemical class 0.000 description 5
- 229920006380 polyphenylene oxide Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 150000002941 palladium compounds Chemical class 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- RHYBFKMFHLPQPH-UHFFFAOYSA-N N-methylhydantoin Chemical compound CN1CC(=O)NC1=O RHYBFKMFHLPQPH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 150000002344 gold compounds Chemical class 0.000 description 2
- 150000001469 hydantoins Chemical class 0.000 description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- XNYADZUHUHIGRZ-UHFFFAOYSA-N propane-1,1,3-triamine Chemical compound NCCC(N)N XNYADZUHUHIGRZ-UHFFFAOYSA-N 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical class NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RFTORHYUCZJHDO-UHFFFAOYSA-N 1,3-dimethylimidazolidine-2,4-dione Chemical compound CN1CC(=O)N(C)C1=O RFTORHYUCZJHDO-UHFFFAOYSA-N 0.000 description 1
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
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- 229910000531 Co alloy Inorganic materials 0.000 description 1
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- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical class [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
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- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical class Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
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- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
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- 235000002906 tartaric acid Nutrition 0.000 description 1
- 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 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Description
本発明は、クロム酸−硫酸混液によるエッチング処理の後処理剤、及び該後処理剤を用いる樹脂成形品に対するめっき方法に関する。 The present invention relates to a post-treatment agent for etching treatment with a chromic acid-sulfuric acid mixture, and a plating method for a resin molded article using the post-treatment agent.
従来、樹脂成形品に対してめっき皮膜を形成する方法としては、脱脂、エッチング、中和の各処理を行った後、無電解めっき用の触媒を樹脂成形品の表面に付与し、その後、無電解めっきを行い、更に必要に応じて電気めっきを行う方法が一般的な方法である。 Conventionally, as a method of forming a plating film on a resin molded product, after performing degreasing, etching, and neutralization treatment, a catalyst for electroless plating is applied to the surface of the resin molded product, and thereafter A general method is a method in which electrolytic plating is performed, and electroplating is performed as necessary.
この様なめっき方法では、例えば、ＡＢＳ樹脂などからなる成形品を被めっき物とする場合には、クロム酸と硫酸を含有する水溶液、いわゆるクロム酸−硫酸混液をエッチング処理液として用いることが多く、エッチング処理後には、通常、樹脂表面上に付着したクロム酸を除去するために、塩酸水溶液を用いた中和処理が行われている。 In such a plating method, for example, when a molded article made of an ABS resin or the like is used as an object to be plated, an aqueous solution containing chromic acid and sulfuric acid, a so-called chromic acid-sulfuric acid mixed solution is often used as an etching treatment liquid. After the etching treatment, neutralization treatment using a hydrochloric acid aqueous solution is usually performed to remove chromic acid adhering to the resin surface.
しかしながら、塩酸水溶液を用いる中和処理方法では、クロム酸の中和が不十分となることがあり、特に、長期間処理液を用いると、クロム酸などの不純物の持ち込みや処理液濃度の変動などによって塩酸水溶液の中和処理能力が低下し易い。このためクロム酸の中和が不十分となり、その影響で触媒能力が低下してめっき皮膜の析出不良が生じ易くなる。 However, the neutralization treatment method using an aqueous hydrochloric acid solution may result in insufficient neutralization of chromic acid. In particular, when a treatment liquid is used for a long period of time, the introduction of impurities such as chromic acid or fluctuations in the concentration of the treatment liquid. As a result, the neutralizing ability of the aqueous hydrochloric acid solution tends to decrease. For this reason, neutralization of chromic acid becomes insufficient, and the catalytic ability is lowered due to the influence of the neutralization.
また、樹脂成形品に対する電気めっき方法として、貴金属化合物及び第一錫化合物を含有するコロイド溶液を用いて触媒を付与した後、糖類を還元剤として含む無電解銅めっき液を用いて薄い導電性皮膜を形成し、その後電気めっきを行う方法が知られている（下記特許文献１参照）。この方法によれば、簡単な処理工程によって短時間に均一な電気めっき皮膜を形成することが可能であるが、やはりエッチング処理液としてクロム酸−硫酸混液を用いる場合には、クロム酸の中和処理が不十分であると、めっきの析出不良が生じ易くなる。 In addition, as an electroplating method for resin molded products, a thin conductive film is formed using an electroless copper plating solution containing a saccharide as a reducing agent after applying a catalyst using a colloidal solution containing a noble metal compound and a stannous compound. A method is known in which electroplating is performed thereafter (see Patent Document 1 below). According to this method, it is possible to form a uniform electroplating film in a short time by a simple treatment process. However, when a chromic acid-sulfuric acid mixture is used as an etching treatment liquid, the chromic acid is neutralized. If the treatment is insufficient, plating deposition defects are likely to occur.
一方、ＡＢＳ樹脂等のスチレン系樹脂以外の樹脂、例えば、ポリフェニレンオキサイド樹脂やこれを含むポリマーアロイなどは、耐熱性や機械特性に優れたエンジニアリングプラスチックスとして注目されているが、クロム酸−硫酸混液によるエッチング処理を行うだけでは、密着性や外観などの良好なめっき皮膜を形成することは困難である。
本発明の主な目的は、クロム酸−硫酸混液によるエッチング工程を含むめっき処理方法において、エッチング処理液に含まれるクロム酸に対して安定した中和作用を有し、且つ、各種の樹脂成形品に対して優れた触媒付着能力を発揮できる新規な処理剤を提供することである。 The main object of the present invention is a plating method including an etching step using a chromic acid-sulfuric acid mixed solution, which has a stable neutralizing action on chromic acid contained in the etching treatment solution, and various resin molded products. It is to provide a novel treating agent capable of exhibiting excellent catalyst adhesion ability.
本発明の更に他の目的は、樹脂成形品に対して析出性、密着性などに優れためっき皮膜を形成することが可能な、上記処理剤を用いるめっき処理方法を提供することである。 Still another object of the present invention is to provide a plating method using the above-described treatment agent, which can form a plating film excellent in precipitation and adhesion on a resin molded product.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、クロム酸−硫酸混液をエッチング処理液として用いるめっき処理方法において、アミン化合物を含有する水溶液をエッチング処理の後処理剤として用いる場合には、安定した中和処理が可能となり、長期間継続して良好なめっき皮膜を形成できることを見出した。更に、該後処理剤を用いる場合には、触媒の付着性が向上し、従来、クロム酸−硫酸混液によるエッチング処理では良好なめっき皮膜を形成することが困難であるとされていたエンジニアリングプラスチックなどの各種の樹脂成形品に対しても、良好なめっき皮膜を形成することが可能となることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, in a plating method using a chromic acid-sulfuric acid mixed solution as an etching treatment solution, when an aqueous solution containing an amine compound is used as a post-treatment agent for the etching treatment, a stable neutralization treatment is possible, which continues for a long time. And found that a good plating film can be formed. Furthermore, when the post-treatment agent is used, the adhesion of the catalyst is improved, and engineering plastics that have been conventionally considered difficult to form a good plating film by etching with a chromic acid-sulfuric acid mixture. The present inventors have found that it is possible to form a good plating film even for the various resin molded products, and have completed the present invention.
即ち、本発明は、下記のクロム酸−硫酸混液によるエッチング処理の後処理剤、及び該後処理剤を用いる樹脂成形品に対するめっき方法を提供するものである。
１． アミン化合物を含有する水溶液からなる、クロム酸−硫酸混液によるエッチング処理の後処理剤。
２． アミン化合物が、一般式：Ｈ２Ｎ（ＣＨ２ＣＨ２ＮＨ）ｎＨ（式中、ｎは１〜１２の数値である）で表されるエチレンアミン類、ポリエチレンイミン類、及び一般式：
That is, the present invention provides a post-treatment agent for etching treatment using the following chromic acid-sulfuric acid mixture, and a plating method for a resin molded article using the post-treatment agent.
1. An aftertreatment agent for etching treatment with a chromic acid-sulfuric acid mixture, which comprises an aqueous solution containing an amine compound.
2. Amine compound has the general formula: (wherein, n is a number of 1~12) H 2 N (CH 2 CH 2 NH) n H ethyleneamines represented by, polyethyleneimines, and the general formula:
（式中、Ｒ１は、プロピル基又は窒素原子上に置換基を有することのあるアミノプロピル基であり、Ｒ２は、プロピル基、窒素原子上に置換基を有することのあるアミノプロピル基又は水素原子である。）で表されるプロピルアミン類からなる群から選ばれた少なくとも一種の化合物である上記項１に記載の後処理剤。
３． 樹脂成形品に対してクロム酸−硫酸混液を用いてエッチング処理を行った後、該樹脂成形品を上記項１又は２に記載の後処理剤に接触させ、その後、触媒付与及び無電解めっきを行い、更に、必要に応じて電気めっきを行うことを特徴とする樹脂成形品に対するめっき方法。
４． 下記の処理工程を含む樹脂成形品に対するめっき方法：
（１）クロム酸−硫酸混液を樹脂成形品に接触させてエッチング処理を行う工程、
（２）上記（１）工程でエッチング処理を行った樹脂成形品を上記項１又は２に記載の後処理剤に接触させる工程、
（３）上記（２）工程で後処理を行った樹脂成形品を、貴金属化合物及び第一錫化合物を含有するコロイド溶液に接触させて、該樹脂成形品に無電解めっき用触媒を付与する工程、
（４）銅化合物、還元性を有する糖類、錯化剤及びアルカリ金属水酸化物を含有する無電解めっき液を用いて、上記（３）工程で無電解めっき用触媒を付与した樹脂成形品に導電性皮膜を形成する工程、
（５）上記（４）工程で導電性皮膜を形成した樹脂成形品に電気めっきを行う工程。
(Wherein R 1 is a propyl group or an aminopropyl group that may have a substituent on the nitrogen atom, and R 2 is an propyl group, an aminopropyl group that may have a substituent on the nitrogen atom, or The post-treatment agent according to Item 1, which is at least one compound selected from the group consisting of propylamines represented by:
3. After etching the resin molded product using a chromic acid-sulfuric acid mixed solution, the resin molded product is brought into contact with the post-treatment agent according to the above item 1 or 2, and thereafter, catalyst application and electroless plating are performed. And a plating method for a resin molded product, wherein electroplating is performed as necessary.
4). Plating method for resin molded product including the following processing steps:
(1) A step of performing an etching process by bringing a chromic acid-sulfuric acid mixture into contact with a resin molded product,
(2) The step of bringing the resin molded product subjected to the etching treatment in the step (1) into contact with the post-treatment agent according to the item 1 or 2,
(3) A step of bringing the resin molded article after the post-treatment in the above step (2) into contact with a colloidal solution containing a noble metal compound and a stannous compound to give an electroless plating catalyst to the resin molded article. ,
(4) A resin molded product provided with an electroless plating catalyst in the step (3) using an electroless plating solution containing a copper compound, a reducing saccharide, a complexing agent and an alkali metal hydroxide. Forming a conductive film;
(5) A step of electroplating the resin molded product on which the conductive film is formed in the step (4).
本発明の後処理剤は、クロム酸−硫酸混塩を用いて樹脂成形品に対してエッチング処理を行う際に、エッチング処理の後処理剤として使用されるものである。通常は、エッチング処理を行った後、水洗を行い、その後、被処理物である樹脂成形品を本発明の後処理剤に接触させることによって、エッチング処理の後処理を行うことができる。 The post-treatment agent of the present invention is used as a post-treatment agent for etching treatment when an etching treatment is performed on a resin molded article using a chromic acid-sulfuric acid mixed salt. Usually, after the etching treatment is performed, washing with water is performed, and then the post-treatment of the etching treatment can be performed by bringing the resin molded product as the object to be treated into contact with the post-treatment agent of the present invention.
樹脂成形品
処理対象となる樹脂成形品の種類については特に限定はなく、クロム酸−硫酸混液によってエッチング処理が可能な樹脂素材からなるものであればよい。代表例としては、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ）樹脂、アクリロニトリル−アクリルゴム−スチレン共重合体（ＡＡＳ）樹脂、アクリロニトリル−エチレンプロピレンゴム−スチレン共重合体（ＡＥＳ）樹脂等のスチレン系樹脂等を挙げることができる。
There is no particular limitation on the kind of the resin molded article comprising a resin molded article processed, chromic acid - may be formed of any resin material which can be etched with sulfuric acid mixture. Typical examples include styrene-based resins such as acrylonitrile-butadiene-styrene copolymer (ABS) resin, acrylonitrile-acrylic rubber-styrene copolymer (AAS) resin, acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES) resin, and the like. Examples thereof include resins.
更に、従来の処理工程を採用する場合には、クロム酸−硫酸混液によるエッチングでは、良好なめっき皮膜を形成することが難しいとされていた、ポリフェニレンエーテル樹脂、ポリフェニレンオキサイド樹脂などのエンジニアリングプラスチックに対しても、本発明の後処理剤を用いることによって、良好なめっき皮膜を形成することができる。 Furthermore, when employing a conventional processing process, it is difficult to form an excellent plating film by etching with a chromic acid-sulfuric acid mixed solution. For engineering plastics such as polyphenylene ether resin and polyphenylene oxide resin, etc. However, a favorable plating film can be formed by using the post-treatment agent of the present invention.
エッチング処理
エッチング処理に用いるクロム酸−硫酸混液としては、通常、樹脂成形品に対するエッチング処理液として用いられているものを用いることができる。例えば、クロム酸−硫酸混液の代表例としては、クロム酸３６０〜４２０ｇ／Ｌ程度と硫酸３６０〜４２０ｇ／Ｌ程度を含有する水溶液を挙げることができる。
Etching treatment As the chromic acid-sulfuric acid mixed solution used for the etching treatment, those usually used as an etching treatment solution for a resin molded product can be used. For example, a representative example of the chromic acid-sulfuric acid mixed solution includes an aqueous solution containing about 360 to 420 g / L of chromic acid and about 360 to 420 g / L of sulfuric acid.
エッチング処理方法については特に限定はなく、常法に従って樹脂成形品の被処理面をエッチング処理液に接触させればよい。通常は、エッチング処理液中に樹脂成形品を浸漬する方法によって処理すればよい。処理条件についても常法に従えばよく、例えば、浸漬法にて処理を行う場合には、液温を６０〜７０℃程度とすることが好ましい。浸漬時間については特に限定はなく、エッチング処理の進行によって適宜決めれば良く、通常、５〜１５分程度の浸漬時間とすれば良い。 There is no particular limitation on the etching treatment method, and the treated surface of the resin molded article may be brought into contact with the etching treatment liquid according to a conventional method. Usually, it may be processed by a method of immersing a resin molded product in an etching processing solution. The treatment conditions may be in accordance with ordinary methods. For example, when treatment is performed by an immersion method, the liquid temperature is preferably about 60 to 70 ° C. There is no particular limitation on the immersion time, and it may be determined as appropriate depending on the progress of the etching treatment. Usually, the immersion time may be about 5 to 15 minutes.
後処理剤
本発明の後処理剤は、アミン化合物を含有する水溶液からなるものである。アミン化合物としては、好ましくは、一般式：Ｈ２Ｎ（ＣＨ２ＣＨ２ＮＨ）ｎＨ（式中、ｎは１〜１２の数値である）で表されるエチレンアミン類、ポリエチレンイミン類、及び一般式：
Post-treatment agent The post-treatment agent of the present invention comprises an aqueous solution containing an amine compound. The amine compound preferably has the general formula: H 2 N (CH 2 CH 2 NH) n H ( wherein, n is a numerical value of 1 to 12) ethylene amine represented by, polyethyleneimines, and General formula:
（式中、Ｒ１は、プロピル基又は窒素原子上に置換基を有することのあるアミノプロピル基であり、Ｒ２は、プロピル基、窒素原子上に置換基を有することのあるアミノプロピル基又は水素原子である。）で表されるプロピルアミン類からなる群から選ばれた少なくとも一種の化合物を用いることができる。 (Wherein R 1 is a propyl group or an aminopropyl group that may have a substituent on the nitrogen atom, and R 2 is an propyl group, an aminopropyl group that may have a substituent on the nitrogen atom, or It is a hydrogen atom.) At least one compound selected from the group consisting of propylamines represented by:
上記一般式において、プロピル基は、ｎ−プロピル基、イソプロピル基のいずれであっても良い。窒素原子上に置換基を有することのあるアミノプロピル基において、置換基としては、メチル基等の低級アルキル基を例示できる。 In the above general formula, the propyl group may be an n-propyl group or an isopropyl group. In the aminopropyl group that may have a substituent on the nitrogen atom, examples of the substituent include lower alkyl groups such as a methyl group.
これらのアミン化合物の内で、エチレンアミン類としては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等を例示できる。 Among these amine compounds, examples of ethyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
ポリエチレンイミン類は、エチレンイミンを重合した水溶性ポリマーであり、数平均分子量が３００〜７００００程度のものを好適に用いることができ、更に好ましくは数平均分子量が６００〜１００００程度のものを用いることができる。 Polyethyleneimines are water-soluble polymers obtained by polymerizing ethyleneimine, and those having a number average molecular weight of about 300 to 70000 can be suitably used, and more preferably those having a number average molecular weight of about 600 to 10,000 are used. Can do.
プロピルアミン類としては、プロピルアミン、イソプロピルアミン、ジイソプロピルアミン、ジアミノプロピルアミン、メチルアミノプロピルアミン、ジメチルアミノプロピルアミン等を例示できる。これら内で、特に好ましいアミン化合物として、プロピルアミン、イソプロピルアミン、ジアミノプロピルアミン等を挙げることができる。これらのアミン化合物は、一種単独又は二種以上混合して用いることができる。 Examples of propylamines include propylamine, isopropylamine, diisopropylamine, diaminopropylamine, methylaminopropylamine, dimethylaminopropylamine and the like. Among these, particularly preferred amine compounds include propylamine, isopropylamine, diaminopropylamine and the like. These amine compounds can be used singly or in combination of two or more.
本発明の後処理剤におけるアミン化合物の濃度は、０．０１〜５０ｇ／Ｌ程度とすることが好ましく、０．０２〜１０ｇ／Ｌ程度とすることがより好ましい。 The concentration of the amine compound in the post-treatment agent of the present invention is preferably about 0.01 to 50 g / L, and more preferably about 0.02 to 10 g / L.
本発明の後処理剤を用いる後処理方法については特に限定的ではなく、エッチング処理を行った後、水洗を行い、その後、上記した後処理剤に被めっき物を接触させればよい。通常は、該後処理剤中に被めっき物を浸漬することによって効率のよい処理が可能である。後処理の条件についても特に限定的ではないが、例えば、１０〜５０℃程度の後処理剤中に１０秒〜１０分間程度被めっき物を浸漬すればよい。 The post-treatment method using the post-treatment agent of the present invention is not particularly limited, and after performing the etching treatment, washing with water may be performed, and then the object to be plated may be brought into contact with the above-described post-treatment agent. Usually, efficient treatment is possible by immersing an object to be plated in the post-treatment agent. The conditions for the post-treatment are not particularly limited. For example, the object to be plated may be immersed in a post-treatment agent of about 10 to 50 ° C. for about 10 seconds to 10 minutes.
本発明の後処理剤は、ｐＨ値については特に限定されない。ただし、処理対象となる樹脂成形品が、めっきを析出させない部分を含む２種類の樹脂から形成されている場合や、樹脂成形品の非めっき部分にめっき用レジスト皮膜が形成されている場合等には、目的とする樹脂表面にのみめっき皮膜を選択的に析出させることが必要となる。このような場合には、ｐＨを１２程度以下とすることが好ましく、８程度以下とすることがより好ましい。ｐＨの下限値については、特に限定的ではないが、４程度とすることが好ましい。この様なｐＨ範囲とすることによって、選択性良くめっき皮膜を形成することが可能となる。ｐＨを上記範囲に調整する場合には、エッチング液の持ち込みによるｐＨの変動を抑制するために、更に、緩衝剤を添加しても良い。緩衝剤としては、炭酸、ほう酸、りん酸、亜りん酸、しゅう酸、酢酸、マロン酸、りんご酸、くえん酸、グリコール酸、グルコン酸、こはく酸、グリシン、ニトリロジ酢酸、ニトリロトリ酢酸、２−アミノエタノール、ジエタノールアミン、トリエタノールアミンおよびこれらの塩類等を例示できる。これらのうち一種単独又は二種以上混合して用いることができる。 The post-treatment agent of the present invention is not particularly limited with respect to the pH value. However, when the resin molded product to be processed is formed from two types of resin including a portion that does not deposit plating, or when a plating resist film is formed on the non-plated portion of the resin molded product, etc. It is necessary to selectively deposit a plating film only on the target resin surface. In such a case, the pH is preferably about 12 or less, more preferably about 8 or less. The lower limit of pH is not particularly limited, but is preferably about 4. By setting it as such a pH range, it becomes possible to form a plating film with sufficient selectivity. In the case of adjusting the pH to the above range, a buffering agent may be further added in order to suppress the change in pH due to bringing in the etching solution. Buffers include carbonic acid, boric acid, phosphoric acid, phosphorous acid, oxalic acid, acetic acid, malonic acid, malic acid, citric acid, glycolic acid, gluconic acid, succinic acid, glycine, nitrodiacetic acid, nitrilotriacetic acid, 2-amino Examples include ethanol, diethanolamine, triethanolamine, and salts thereof. Among these, it can use individually by 1 type or in mixture of 2 or more types.
緩衝剤の添加量については特に限定的ではないが、通常、１〜５０ｇ／Ｌ程度とすることが好ましい。 The addition amount of the buffering agent is not particularly limited, but is usually preferably about 1 to 50 g / L.
触媒付与及びめっき処理
上記した方法でエッチング処理と、後処理を行った後、無電解めっき用の触媒を付与して無電解めっきを行うことによって、密着性、物性、外観などに優れためっき皮膜を形成することができる。
Catalyst application and plating treatment After performing etching treatment and post-treatment by the above-mentioned method, a plating film excellent in adhesion, physical properties, appearance, etc. by applying a catalyst for electroless plating and performing electroless plating Can be formed.
本発明の後処理剤は、長期間使用した場合にも、中和処理能力の低下が少ないので、公知の方法で触媒付与と無電解めっきを行うことによって、長期間安定して良好なめっき皮膜を形成することができる。更に、クロム酸−硫酸混液によるエッチング処理では良好なめっき皮膜を形成することが困難とされていたポリフェニレンオキサイド樹脂からなる樹脂成形品に対しても、触媒の付着性が向上して均一に触媒核を付着させることができ、良好なめっき皮膜を形成することが可能となる。 Since the post-treatment agent of the present invention has little decrease in neutralizing ability even when used for a long period of time, by applying a catalyst and electroless plating by a known method, a stable and good plating film for a long period of time Can be formed. Furthermore, even for resin molded products made of polyphenylene oxide resin, which is difficult to form a good plating film by etching with a mixed solution of chromic acid-sulfuric acid, the adhesion of the catalyst is improved and the catalyst core is uniformly formed. It is possible to form a good plating film.
触媒付与処理の具体的な方法としては、無電解めっき皮膜を形成する際に行われている公知の方法をいずれも適用できる。一般的には、パラジウムを付与する方法が広く行われており、例えば、センシタイジング−アクチベーション法、キャタリスト−アクセレーター法、アルカリキャタリスト法等により触媒を付与すればよい。尚、必要に応じて、常法に従ってプリディップ処理などを行ってもよい。 As a specific method of the catalyst application treatment, any known method that is used when forming an electroless plating film can be applied. In general, a method for imparting palladium is widely performed. For example, a catalyst may be imparted by a sensitizing-activation method, a catalyst-accelerator method, an alkaline catalyst method, or the like. In addition, you may perform a pre-dip process etc. according to a conventional method as needed.
更に、無電解めっき皮膜を形成する際に用いられるその他の触媒、例えば、鉄、コバルト、ニッケル、白金等の触媒金属を付与してもよい。また、上記した触媒金属を二種類以上併用してもよい。例えば、Ｓｎ−Ａｇ触媒（奥野製薬工業（株）、ＭＯＯＮプロセス）、Ｓｎ−Ａｇ−Ｐｄ触媒（奥野製薬工業（株）、テクノクリアプロセス）などを適用できる。 Furthermore, you may provide other catalysts used when forming an electroless-plating film, for example, catalytic metals, such as iron, cobalt, nickel, and platinum. Two or more kinds of the above-described catalyst metals may be used in combination. For example, Sn-Ag catalyst (Okuno Pharmaceutical Co., Ltd., MOON process), Sn-Ag-Pd catalyst (Okuno Pharmaceutical Co., Ltd., Techno Clear Process), etc. can be applied.
無電解めっき液としては、公知の自己触媒性の無電解めっき液であれば特に限定なく使用できる。この様な無電解めっき液としては、無電解ニッケルめっき液、無電解銅めっき液、無電解コバルトめっき液、無電解ニッケル−コバルト合金めっき液、無電解金めっき液等を例示できる。 As the electroless plating solution, any known self-catalytic electroless plating solution can be used without any particular limitation. Examples of such an electroless plating solution include an electroless nickel plating solution, an electroless copper plating solution, an electroless cobalt plating solution, an electroless nickel-cobalt alloy plating solution, and an electroless gold plating solution.
無電解めっきの条件については、公知の方法と同様とすればよい。また、必要に応じて無電解めっき皮膜を二層以上形成してもよい。 The conditions for electroless plating may be the same as known methods. Moreover, you may form two or more layers of an electroless-plating film as needed.
また、無電解めっき皮膜を形成した後、必要に応じて、電気めっきを行うことができる。この場合、無電解めっきの後、必要に応じて、酸、アルカリ等の水溶液によって活性化処理を行い、その後、電気めっきを行えばよい。電気めっき液の種類については特に限定はなく、公知の電気めっき液から目的に応じて適宜選択すればよい。 Moreover, after forming an electroless-plating film | membrane, electroplating can be performed as needed. In this case, after electroless plating, if necessary, activation treatment may be performed with an aqueous solution of acid, alkali, etc., and then electroplating may be performed. There is no limitation in particular about the kind of electroplating liquid, What is necessary is just to select suitably according to the objective from well-known electroplating liquid.
めっき処理工程
本発明の後処理剤による後処理を含むめっき処理工程の一例として、還元性を有する糖類を還元剤として含む無電解銅めっき液を用いる処理工程を以下に示す。このめっき処理工程によれば、触媒付与後のアクセレーション（活性化工程）や導電性皮膜（無電解銅めっき皮膜）形成後の活性化処理が不要となり、処理効率が向上する。また、使用する無電解銅めっき液の安定性が良好であり、更に、形成される導電性皮膜（無電解銅めき皮膜）に欠陥が少ないために外観、物性などが良好な電気めっき皮膜を安定して形成できる。また、無電解銅めっき液の還元剤として比較的還元力の弱い糖類を用いるために、めっき用治具への無電解銅めっきの析出がほとんどなく、めっき用治具を交換することなく、無電解めっき処理と電気めっき処理を連続して行うことが可能となる。
Plating treatment process As an example of the plating treatment process including the post-treatment with the post-treatment agent of the present invention, a treatment process using an electroless copper plating solution containing a reducing sugar as a reducing agent is shown below. According to this plating treatment step, the acceleration after activation of the catalyst (activation step) and the activation treatment after the formation of the conductive film (electroless copper plating film) are not required, and the treatment efficiency is improved. In addition, the electroless copper plating solution used has good stability, and the electroconductive film (electroless copper plating film) that is formed has few defects. Can be formed. In addition, since saccharides with relatively low reducing power are used as the reducing agent for the electroless copper plating solution, there is almost no deposition of electroless copper plating on the plating jig, and there is no need to replace the plating jig. The electrolytic plating process and the electroplating process can be performed continuously.
以下、このめっき処理工程について具体的に説明する。
（１）エッチング及び後処理工程
エッチング処理工程と後処理工程については、エッチング処理液としてクロム酸−硫酸混液を用い、後処理液としてアミン化合物を含有する水溶液を用いて、上記した処理方法と同様にして各々の処理を行えばよい。尚、エッチング処理に先立って、必要に応じて、常法に従って、脱脂などの前処理を行うことができる。
Hereinafter, this plating process will be specifically described.
(1) Etching and post-treatment process The etching treatment step and the post-treatment step are the same as the above-described treatment method using a chromic acid-sulfuric acid mixed solution as an etching treatment liquid and an aqueous solution containing an amine compound as a post-treatment liquid. Each process may be performed as follows. Prior to the etching treatment, a pretreatment such as degreasing can be performed according to a conventional method, if necessary.
（２）触媒付与工程
次いで、無電解めっき用の触媒液として、貴金属化合物及び第一錫化合物を含有するコロイド溶液を用いて、被処理物に無電解めっき用触媒を付与する。触媒液として用いるコロイド溶液としては、無電解めっき用の触媒液として公知のものを使用できる。この様な公知の触媒液は、通常、無電解めっきに対する触媒能を有する化合物として知られている白金化合物、金化合物、パラジウム化合物、銀化合物等の貴金属化合物を含有するものである。この様な触媒液に配合される白金化合物の具体例としては塩化白金塩等、金化合物の具体例としては塩化金塩、亜硫酸金塩等、パラジウム化合物の具体例としては塩化パラジウム、硫酸パラジウム等、銀化合物の具体例としては硝酸銀、硫酸銀等を挙げることができる。貴金属化合物は、一種単独又は二種以上混合して用いることができる。本発明では、特に、貴金属化合物としてパラジウム化合物を含有する触媒液を用いることが好ましい。貴金属化合物の配合量については、特に限定的ではないが、通常、金属量として１００〜５００ｍｇ／Ｌ程度の範囲が好適である。
(2) Catalyst application step Next, a catalyst for electroless plating is applied to an object to be treated using a colloid solution containing a precious metal compound and a stannous compound as a catalyst solution for electroless plating. As the colloidal solution used as the catalyst solution, those known as a catalyst solution for electroless plating can be used. Such a known catalyst solution usually contains a noble metal compound such as a platinum compound, a gold compound, a palladium compound, or a silver compound, which is known as a compound having catalytic ability for electroless plating. Specific examples of platinum compounds to be blended in such a catalyst solution include platinum chloride salts and the like, specific examples of gold compounds include gold chloride salts and gold sulfites, and specific examples of palladium compounds include palladium chloride and palladium sulfate. Specific examples of the silver compound include silver nitrate and silver sulfate. A noble metal compound can be used individually by 1 type or in mixture of 2 or more types. In the present invention, it is particularly preferable to use a catalyst solution containing a palladium compound as the noble metal compound. The compounding amount of the noble metal compound is not particularly limited, but usually a range of about 100 to 500 mg / L as the metal amount is suitable.
上記コロイド溶液に配合する第一錫化合物としては、塩化第一錫、硫酸第一錫等が好ましく、これらを一種単独又は適宜混合して配合することができる。特に、塩化第一錫が好ましい。第一錫化合物の配合量は、通常、錫金属として１０〜５０ｇ／Ｌ程度で、貴金属量の５０〜１２０重量倍程度とすればよい。 As the stannous compound to be blended in the colloidal solution, stannous chloride, stannous sulfate and the like are preferable, and these can be blended alone or in combination as appropriate. In particular, stannous chloride is preferred. The blending amount of the stannous compound is usually about 10 to 50 g / L as tin metal, and may be about 50 to 120 times the precious metal amount.
上記コロイド溶液は、一般に、ｐＨ１程度以下の強酸性のコロイド溶液であり、常法に従って製造することができる。例えば、貴金属化合物と第一錫化合物を、それぞれ別個に酸溶液に溶解し、これらの溶液を混合してコロイド溶液とし、使用時に適度な濃度に調整して用いることができる。この際に用いる酸溶液としては、塩酸溶液、硫酸溶液、塩酸と硫酸の混酸、塩化ナトリウムを含有する塩酸、塩化ナトリウムを含有する硫酸、塩化ナトリウムを含有する塩酸と硫酸の混酸等が挙げられる。 The colloidal solution is generally a strongly acidic colloidal solution having a pH of about 1 or less, and can be produced according to a conventional method. For example, a noble metal compound and a stannous compound can be separately dissolved in an acid solution, and these solutions can be mixed to form a colloidal solution, which can be adjusted to an appropriate concentration when used. Examples of the acid solution used in this case include hydrochloric acid solution, sulfuric acid solution, mixed acid of hydrochloric acid and sulfuric acid, hydrochloric acid containing sodium chloride, sulfuric acid containing sodium chloride, mixed acid of hydrochloric acid and sulfuric acid containing sodium chloride, and the like.
上記コロイド溶液には、更に、必要に応じて、低級脂肪族モノカルボン酸銅、臭化銅等を配合してもよい。特に、銅化合物については、溶解性が良好であること等から、２価の銅化合物を用いることが好ましい。また、低級脂肪族モノカルボン酸銅のうちでは、ギ酸銅、酢酸銅等が好ましく、これらを用いることによって、安定なコロイド溶液が形成されて、均一なコロイド膜として被処理物に付着させ易くなる。銅化合物の配合量は、銅金属として０．２〜３ｇ／Ｌ程度が好ましく、０．５〜２ｇ／Ｌ程度がより好ましい。 If necessary, the colloidal solution may further contain lower aliphatic monocarboxylic acid copper, copper bromide or the like. In particular, with respect to the copper compound, it is preferable to use a divalent copper compound because of its good solubility. Of the lower aliphatic monocarboxylic acid coppers, copper formate, copper acetate, and the like are preferable. By using these, a stable colloidal solution is formed, and it becomes easy to adhere to an object to be processed as a uniform colloidal film. . The amount of the copper compound is preferably about 0.2 to 3 g / L, more preferably about 0.5 to 2 g / L as copper metal.
特に、パラジウム化合物をパラジウム金属量として１５０〜３００ｐｐｍ程度含有し、第一錫化合物を錫金属量として１０〜２２ｇ／Ｌ程度含有する塩酸水溶液を触媒液として用いることが好ましい。 In particular, an aqueous hydrochloric acid solution containing about 150 to 300 ppm of the palladium compound as the amount of palladium metal and about 10 to 22 g / L of the stannous compound as the amount of tin metal is preferably used as the catalyst solution.
コロイド溶液による処理方法としては、通常、１０〜５０℃程度、好ましくは、２５〜４５℃程度のコロイド溶液中に、被処理物を２〜１０分程度、好ましくは３〜５分程度浸漬すればよい。この処理により、被処理物の表面に均一な触媒膜を付着させることができる。 As a treatment method using a colloidal solution, the treatment object is usually immersed in a colloidal solution at about 10 to 50 ° C., preferably about 25 to 45 ° C. for about 2 to 10 minutes, preferably about 3 to 5 minutes. Good. By this treatment, a uniform catalyst film can be attached to the surface of the workpiece.
（３）めっき工程：
次いで、触媒を付与した樹脂成形品に、無電解銅めっき液を用いて導電性を有する皮膜を形成する。
(3) Plating process:
Next, a conductive film is formed on the resin molded product provided with the catalyst using an electroless copper plating solution.
無電解銅めっき液としては、銅化合物、還元性を有する糖類、錯化剤及びアルカリ金属水酸化物を含有する無電解銅めっき液を用いる。 As the electroless copper plating solution, an electroless copper plating solution containing a copper compound, a reducing sugar, a complexing agent and an alkali metal hydroxide is used.
上記無電解銅めっき液では、銅化合物としては、硫酸銅、塩化銅、炭酸銅、酸化銅、水酸化銅等を使用できる。銅化合物の含有量は、銅金属量として０．１〜５ｇ／Ｌ程度、好ましくは０．８〜１．２ｇ／Ｌ程度とすればよい。 In the electroless copper plating solution, copper sulfate, copper chloride, copper carbonate, copper oxide, copper hydroxide, etc. can be used as the copper compound. The content of the copper compound may be about 0.1 to 5 g / L, preferably about 0.8 to 1.2 g / L as the amount of copper metal.
上記無電解銅めっき液に配合する還元性のある糖類の具体例としては、ブドウ糖、グルコース、ソルビット、セルロース、ショ糖、マンニット、グルコノラクトン等を挙げることができる。糖類の含有量は３〜５０ｇ／Ｌ程度とし、好ましくは１０〜２０ｇ／Ｌ程度とする。 Specific examples of reducing saccharides to be blended in the electroless copper plating solution include glucose, glucose, sorbit, cellulose, sucrose, mannitol, gluconolactone, and the like. The saccharide content is about 3 to 50 g / L, preferably about 10 to 20 g / L.
該無電解銅めっき液に配合する錯化剤としては、ヒダントイン類、有機カルボン酸類等を用いることができる。ヒダントイン類の具体例としては、ヒダントイン、１−メチルヒダントイン、１，３−ジメチルヒダントイン、５，５−ジメチルヒダントイン、アラントイン等を挙げることができ、有機カルボン酸類の具体例としては、クエン酸、酒石酸、コハク酸及びこれらの塩類等を挙げることができる。錯化剤は、一種単独又は二種以上混合して用いることができる。錯化剤の配合量は、２〜５０ｇ／Ｌ程度とし、好ましくは１０〜４０ｇ／Ｌ程度とする。 As complexing agents to be blended in the electroless copper plating solution, hydantoins, organic carboxylic acids and the like can be used. Specific examples of hydantoins include hydantoin, 1-methylhydantoin, 1,3-dimethylhydantoin, 5,5-dimethylhydantoin, and allantoin. Specific examples of organic carboxylic acids include citric acid and tartaric acid. And succinic acid and salts thereof. Complexing agents can be used singly or in combination of two or more. The compounding amount of the complexing agent is about 2 to 50 g / L, preferably about 10 to 40 g / L.
上記無電解銅めっき液には、更に、アルカリ金属水酸化物を配合することが必要である。アルカリ金属水酸化物としては、入手の容易性、コストなどの点から、水酸化ナトリウム、水酸化カリウム、水酸化リチウム等を用いることが適当である。アルカリ金属水酸化物は、一種単独又は適宜混合して用いることができる。アルカリ金属水酸化物の配合量は、１０〜８０ｇ／Ｌ程度とすることが好ましく、３０〜５０ｇ／Ｌ程度とすることがより好ましい。 The electroless copper plating solution needs to further contain an alkali metal hydroxide. As the alkali metal hydroxide, it is appropriate to use sodium hydroxide, potassium hydroxide, lithium hydroxide or the like from the viewpoints of availability and cost. An alkali metal hydroxide can be used individually by 1 type or in mixture as appropriate. The blending amount of the alkali metal hydroxide is preferably about 10 to 80 g / L, and more preferably about 30 to 50 g / L.
尚、該無電解銅めっき液では、上記した各成分の配合割合の範囲内において、めっき浴のｐＨが１０．０〜１４．０の範囲、好ましくは１１．５〜１３．５の範囲となるように、使用成分の組み合わせ、具体的な配合割合などを適宜調整することが好ましい。 In the electroless copper plating solution, the pH of the plating bath is in the range of 10.0 to 14.0, preferably in the range of 11.5 to 13.5, within the range of the blending ratio of each component described above. Thus, it is preferable to appropriately adjust the combination of the components used and the specific blending ratio.
上記無電解めっき液には、更に、必要に応じて、安定剤として黄血塩、ロダン塩等を配合できるが、特に、該無電解めっき液は、安定性が非常に良好であるので、安定剤を使用しないか、又は安定剤を使用する場合にも、非常に弱い安定剤であるタンニン酸、ロダニン等を数ｍｇ／Ｌ程度の少量配合するだけで、良好な安定性を維持できる。 The electroless plating solution may further contain a yellow blood salt, a rhodan salt, or the like as a stabilizer, if necessary. In particular, the electroless plating solution has a very good stability, so that it is stable. Even when an agent is not used or a stabilizer is used, good stability can be maintained only by adding a very small amount of tannic acid, rhodanine, etc., which are very weak stabilizers, of a few mg / L.
無電解めっき液による処理工程では、無電解銅めっき液の液温を、２０〜７０℃程度、好ましくは３５〜５０℃程度とし、このめっき液中に被処理物を３０秒〜２０分程度、好ましくは３〜５分程度浸漬すればよい。 In the treatment step with the electroless plating solution, the temperature of the electroless copper plating solution is about 20 to 70 ° C., preferably about 35 to 50 ° C., and the object to be treated is placed in this plating solution for about 30 seconds to 20 minutes, Preferably, it may be immersed for about 3 to 5 minutes.
この工程により、被処理物の表面に非常に薄い膜厚の導電性皮膜が形成され、この皮膜上に直接電気めっきを行うことが可能となる。 By this step, a very thin conductive film is formed on the surface of the object to be processed, and it is possible to perform electroplating directly on this film.
次いで、常法に従って被処理物を電気めっき処理に供する。電気めっき浴の種類は、特に限定されるものではなく、従来公知のいずれの電気めっき浴も使用可能である。又、めっき処理の条件も常法に従えばよい。 Next, the object to be processed is subjected to an electroplating process according to a conventional method. The type of the electroplating bath is not particularly limited, and any conventionally known electroplating bath can be used. Moreover, the conditions for the plating treatment may be in accordance with a conventional method.
本発明によれば、樹脂成形品に対してクロム酸−硫酸混液を用いてエッチング処理を行う場合に、塩酸水溶液による中和処理では、処理液の処理能力不足や処理能力の低下によって生じ易かっためっき析出不良を改善して、安定して良好なめっき皮膜を形成することが可能となる。 According to the present invention, when an etching treatment is performed on a resin molded product using a chromic acid-sulfuric acid mixed solution, the neutralization treatment with an aqueous hydrochloric acid solution is likely to occur due to insufficient treatment capacity of the treatment liquid or a reduction in treatment ability. It is possible to improve the plating deposition failure and stably form a good plating film.
また、これまでは良好なめっき皮膜を形成することが困難であった樹脂素材、例えばポニフェニレンオキサイド樹脂等に対しても密着性、外観、物性などに優れた良好なめっき皮膜を形成することが可能となる。 In addition, it is possible to form a good plating film excellent in adhesion, appearance, physical properties, etc. even for resin materials that have been difficult to form a good plating film, such as poniphenylene oxide resin. It becomes possible.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
被処理物として、ＡＢＳ樹脂（ＵＭＧ ＡＢＳ(株)製、商標名：サイコラック３００１Ｍ）、ＰＣ／ＡＢＳアロイ樹脂（ＵＭＧ ＡＢＳ（株）製、商標名：ＵＭＧアロイＴＣ−４１Ｍ）及びポリフェニレンオキサイド樹脂（ＧＥプラスチックス（株）製）の各樹脂製の平板（１０ｃｍ×５ｃｍ×厚さ０．３ｃｍ、表面積約１ｄｍ2）を用いた。
Example 1
As an object to be processed, ABS resin (UMG ABS Co., Ltd., trade name: Psycolac 3001M), PC / ABS alloy resin (UMG ABS Co., Ltd., trade name: UMG Alloy TC-41M) and polyphenylene oxide resin ( Each resin flat plate (10 cm × 5 cm × thickness 0.3 cm, surface area about 1 dm 2 ) manufactured by GE Plastics Co., Ltd. was used.
めっき用冶具として被処理物との接点部が２カ所の冶具を使用して、被処理物を冶具にセットした後、アルカリ系脱脂溶液（奥野製薬工業（株）製、商標名：エースクリーンＡ−２２０、５０ｇ／Ｌ水溶液）中に５０℃で５分間浸漬し、水洗した。 Using a jig having two contact points with the workpiece as a plating jig, and setting the workpiece on the jig, an alkaline degreasing solution (Okuno Pharmaceutical Co., Ltd., trade name: Ascreen A) -220, 50 g / L aqueous solution) at 50 ° C. for 5 minutes and washed with water.
その後、無水クロム酸４００ｇ／Ｌ及び硫酸４００ｇ／Ｌを含有する水溶液からなるエッチング溶液に６７℃で１０分間浸漬して、被処理物の表面を粗化した。その後、被処理物を水洗し、後処理剤として下記の本発明浴１〜７又は比較浴を用いて、浴中に２５℃で２分浸漬することによって、エッチングの後処理を行った。
＊後処理剤
本発明浴１：エチレンジアミンを５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
本発明浴２：ジエチレントリアミンを５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
本発明浴３：トリエチレンテトラミンを５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
本発明浴４：テトラエチレンペンタミンを５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
本発明浴５：ペンタエチレンヘキサミンを５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
本発明浴６：数平均分子量６００のポリエチレンイミンを５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
本発明浴７：数平均分子量１２００のポリエチレンイミンを５ｇ／Ｌ、炭酸水素ナトリウム１０ｇ含有するｐＨ８の水溶液
本発明浴８：プロピルアミンを５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
本発明浴９：エチレンジアミンを２．５ｇ／Ｌとテトラエチレンペンタミンを２．５ｇ／Ｌ含有するｐＨ１１〜１２の水溶液
比較浴１：３５％塩酸を５０ｍｌ／Ｌ含有するｐＨ１以下の水溶液。
Thereafter, the surface of the object to be processed was roughened by dipping in an etching solution composed of an aqueous solution containing 400 g / L of chromic anhydride and 400 g / L of sulfuric acid at 67 ° C. for 10 minutes. Thereafter, the object to be treated was washed with water, and after-etching was performed by immersing in the bath at 25 ° C. for 2 minutes using the following inventive baths 1 to 7 or a comparative bath as a post-treatment agent.
* Post-treatment agent Invention bath 1: aqueous solution of pH 11-12 containing 5 g / L of ethylenediamine Invention bath 2: aqueous solution of pH 11-12 containing 5 g / L of diethylenetriamine Invention bath 3: 5 g / L of triethylenetetramine An aqueous solution of pH 11-12 containing the present invention bath 4: An aqueous solution of pH 11-12 containing 5 g / L of tetraethylenepentamine. An inventive bath 5: An aqueous solution of pH 11-12 containing 5 g / L of pentaethylenehexamine. : Aqueous solution of pH 11 to 12 containing 5 g / L of polyethyleneimine having a number average molecular weight of 600. Invention bath 7: aqueous solution of pH 8 containing 5 g / L of polyethyleneimine having a number average molecular weight of 1200 and 10 g of sodium hydrogencarbonate. An aqueous solution of pH 11-12 containing 5 g / L of propylamine. Down the 2.5 g / L of tetraethylene pentamine and 2.5 g / L aqueous solution comparison pH11~12 containing Bath 1, 35 percent aqueous solution of pH1 below containing 50 ml / L hydrochloric acid.
次に、プリディップ処理として、３５％塩酸２５０ｍｌ／Ｌを含有する水溶液に被処理物を２５℃で１分間処理した後、塩化パラジウム３３０ｍｇ／Ｌ、塩化第一錫３５ｇ／Ｌ及び３５％塩酸２５０ｍｌ／Ｌを含有するｐＨ１以下のコロイド溶液からなる触媒付与液中に３５℃で６分間浸漬して、被処理物に均一に触媒を吸着させた。 Next, as a pre-dip treatment, an object to be treated was treated in an aqueous solution containing 35% hydrochloric acid 250 ml / L at 25 ° C. for 1 minute, and then palladium chloride 330 mg / L, stannous chloride 35 g / L and 35% hydrochloric acid 250 ml. The catalyst was uniformly adsorbed on the object to be treated by immersing in a catalyst-imparting solution composed of a colloidal solution containing 1 / L or less of pH 1 at 35 ° C. for 6 minutes.
その後水洗を行い、無電解銅めっき浴（奥野工業（株）製 ＣＲＰセレクター浴）に４５℃で３分浸漬して、導電性皮膜を形成した。 Thereafter, it was washed with water and immersed in an electroless copper plating bath (CRP selector bath manufactured by Okuno Kogyo Co., Ltd.) at 45 ° C. for 3 minutes to form a conductive film.
次いで、充分に水洗し、冶具を変えることなく次工程の電気銅めっきに移行した。電気銅めっき液としては、硫酸銅２５０ｇ／Ｌ、硫酸５０ｇ／Ｌ及び塩素イオン５０ppmを含有する水溶液に、光沢剤として奥野製薬工業（株）製のＣＲＰカッパーＭＵ（商標名）５ｍｌ／ＬとＣＲＰカッパーＡ（商標名）０．５ｍｌ／Ｌを添加しためっき液を用い、含リン銅板を陽極とし、被処理品を陰極として、ゆるやかなエアー撹拌を行いながら、液温２５℃、電流密度１．５Ａ／ｄｍ2で最大５分間電気銅めっきを行い、電気銅めっき皮膜が被処理物の全面をカバーリングするまでの時間を測定した。また、電気銅めっき皮膜の析出状態を目視で観察して、電気銅めっきの析出状態を評価した。被めっき物の全面に均一な銅めっき皮膜が形成されている場合を○として評価した。結果を表１に示す。 Next, it was thoroughly washed with water, and the next step of electrolytic copper plating was performed without changing the jig. As an electrolytic copper plating solution, an aqueous solution containing 250 g / L of copper sulfate, 50 g / L of sulfuric acid and 50 ppm of chloride ions, CRP Copper MU (trade name) 5 ml / L made by Okuno Pharmaceutical Co., Ltd. and CRP as a brightener Using a plating solution to which 0.5 ml / L of copper A (trade name) was added, using a phosphorous copper plate as an anode and a treated product as a cathode, the solution temperature was 25 ° C. and the current density was 1. Electro copper plating was performed at 5 A / dm 2 for a maximum of 5 minutes, and the time until the electro copper plating film covered the entire surface of the object to be treated was measured. Moreover, the deposition state of the electrolytic copper plating film was visually observed to evaluate the deposition state of the electrolytic copper plating. The case where a uniform copper plating film was formed on the entire surface of the object to be plated was evaluated as ○. The results are shown in Table 1.
以上の結果から明らかなように、本発明の後処理剤を用いる場合には、無電解銅めっき処理によって良好な導電性皮膜が形成され、その結果、均一な電気銅めっき皮膜を短時間に形成することができる。また、比較浴である塩酸水溶液による中和処理では均一なめっき皮膜を形成できないポリフェニレンオキサイド樹脂に対しても、本発明の後処理剤で処理することによって、良好な電気銅めっき皮膜を形成することができる。 As is clear from the above results, when the post-treatment agent of the present invention is used, a good conductive film is formed by the electroless copper plating process, and as a result, a uniform electrolytic copper plating film is formed in a short time. can do. In addition, a good electrolytic copper plating film can be formed by treating with the post-treatment agent of the present invention even for polyphenylene oxide resin that cannot form a uniform plating film by neutralization treatment with hydrochloric acid aqueous solution as a comparative bath. Can do.
実施例２
実施例１と同様にして無電解銅めっきまでの処理を行ったＡＢＳ樹脂製平板とＰＣ／ＡＢＳアロイ樹脂製平板を充分に水洗し、乾燥させた後、抵抗率測定器（三菱化学（株）製、商標名：Loresta MP）を用いて樹脂表面の抵抗値を測定した。結果を表２に示す。
Example 2
The ABS resin flat plate and the PC / ABS alloy resin flat plate, which had been processed up to electroless copper plating in the same manner as in Example 1, were thoroughly washed and dried, and then a resistivity meter (Mitsubishi Chemical Corporation). The resistance value of the resin surface was measured by using a trade name: Loresta MP). The results are shown in Table 2.
以上の結果から明らかなように、本発明の後処理剤で処理した場合には、無電解銅めっきの析出性が良好となり、形成される導電性皮膜は抵抗値が低く優れた導電性を有するものとなる。 As is clear from the above results, when treated with the post-treatment agent of the present invention, the electroless copper plating has good deposition properties, and the formed conductive film has low resistance and excellent conductivity. It will be a thing.
Claims (3)
（１）クロム酸−硫酸混液を樹脂成形品に接触させてエッチング処理を行う工程、
（２）上記（１）工程でエッチング処理を行った樹脂成形品を水洗する工程、
（３）上記（２）工程に引き続き、請求項１に記載の中和処理剤に接触させる工程、
（４）上記（３）工程で中和処理を行った樹脂成形品を、貴金属化合物及び第一錫化合物を含有するコロイド溶液に接触させて、該樹脂成形品に無電解めっき用触媒を付与する工程、
（５）銅化合物、還元性を有する糖類、錯化剤及びアルカリ金属水酸化物を含有する無電解めっき液を用いて、上記（４）工程で無電解めっき用触媒を付与した樹脂成形品に導電性皮膜を形成する工程、
（６）上記（５）工程で導電性皮膜を形成した樹脂成形品に電気めっきを行う工程。 Plating method for resin molded product including the following processing steps:
(1) A step of performing an etching process by bringing a chromic acid-sulfuric acid mixture into contact with a resin molded product,
(2) A step of washing the resin molded product that has been subjected to the etching treatment in the step (1),
(3) Following the step (2), the step of contacting the neutralizing agent according to claim 1 ,
(4) The resin molded product that has been neutralized in the step (3) is brought into contact with a colloidal solution containing a noble metal compound and a stannous compound, and a catalyst for electroless plating is imparted to the resin molded product. Process,
(5) A resin molded product provided with a catalyst for electroless plating in the step (4) using an electroless plating solution containing a copper compound, a reducing sugar, a complexing agent and an alkali metal hydroxide. Forming a conductive film;
(6) A step of electroplating the resin molded product on which the conductive film is formed in the step (5).
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