JP6947783B2 - Abs系樹脂表面のめっき前処理方法、及びabs系樹脂表面のめっき処理方法 - Google Patents
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- 238000007747 plating Methods 0.000 title claims description 75
- 229920005989 resin Polymers 0.000 title claims description 58
- 239000011347 resin Substances 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 33
- 238000002203 pretreatment Methods 0.000 title description 10
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 85
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 71
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 37
- 238000007772 electroless plating Methods 0.000 claims description 10
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 10
- 238000009713 electroplating Methods 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 38
- 238000012545 processing Methods 0.000 description 25
- 239000007788 liquid Substances 0.000 description 17
- 239000004094 surface-active agent Substances 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000007788 roughening Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 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 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 238000010306 acid treatment Methods 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- -1 amine salt Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 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
- 229910001431 copper ion Inorganic materials 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
- 230000007423 decrease Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
Description
2CrO 4 2− +2H 3 O + →Cr 2 O 7 2− +3H 2 O
の平衡が存在するものの、Crはいずれにせよ6価である。6価クロムはREACH規制及びRoHS指令の対象ではあるものの、製品内に6価クロムが残留するわけでないので、それ自体が規制を受けるわけではない。しかしながら、近年環境問題への関心が強くなり、6価クロムを使用しない環境調和型技術が強く要望されている。また、Crを含む排水は、還元、中和、凝集沈殿等の排水処理が必要となる上に、沈殿物もCrを含むために容易には廃棄できないという問題点があった。
まず、ヨウ素滴定により処理液(過硫酸溶液S)中に含まれる全酸化剤濃度を測定する。このヨウ素滴定とは、過硫酸溶液SにKIを加えてI2を遊離させ、そのI2をチオ硫酸ナトリウム標準溶液で滴定してI2の量を求め、そのI2の量から酸化剤濃度を求めるものである。次に、過硫酸溶液Sの過酸化水素濃度のみを過マンガン酸カリウム滴定により求め、ヨウ素滴定値から過マンガン酸カリウム滴定値を差し引くことにより過硫酸濃度を算出した。
この試験は、試料を加熱急冷する熱衝撃によって密着性を調べるもので、70℃と−30℃、すなわち温度差100℃をそれぞれの温度を1時間保ち40サイクル実施した後、めっき表面の剥離、クラック、膨れ等の有無などの状況を観察し、下記分類1から3までの3段階で評価する。
分類1:めっきの剥離、クラックやしわ、ふくれが全くない。
分類2:めっきの剥離、クラックやしわ、ふくれが試料面積の25%未満存在する。
分類3:めっきの剥離、クラックやしわ、ふくれが試料面積の25%以上存在する。
図1に示す装置を用いて、ABS系樹脂板8の表面処理を行った。処理槽の仕様及び条件は次の通りである。
処理槽2の容積:40L
ABS系樹脂板8の大きさ:500mm×500mm×厚さ5mm
<過硫酸溶液Sの性状と表面処理条件>
硫酸濃度:75重量%
過硫酸濃度:10g/L
処理温度:75℃
処理時間:15分
<過硫酸生成用電解セル6及び電解条件>
セル容積:0.5L
陽極及び陰極:ダイヤモンド電極(直径150mm)
バイポーラ電極材質:陽極、陰極と同じ
電流密度:50A/dm2
液循環量:2.5L/min
硫酸濃度:75重量%
過硫酸濃度:10g/L
処理温度:75℃
電解硫酸処理条件を表3に示すように種々設定を変更した以外は実施例1と同様にしてクロムめっきを施し、めっきの密着性を評価した。結果を電解硫酸処理条件とともに表3にあわせて示す。
電解硫酸溶液の代わりに、硫酸濃度75重量%の硫酸溶液を用いた以外は実施例1と同様にしてクロムめっきを施し、めっきの密着性を評価した。結果を処理条件とともに表3にあわせて示す。
電解硫酸溶液の代わりに、硫酸と過酸化水素との混合溶液を用いた以外は実施例1と同様にしてクロムめっきを施し、めっきの密着性を評価した。結果を処理条件とともに表3にあわせて示す。
2 処理槽
3 恒温ヒータ
4 配管
5 循環ポンプ
6 電解セル
6A 陽極
6B 陰極
6C バイポーラ電極
7 配管
8 ABS系樹脂板
S 過硫酸溶液
Claims (2)
- 硫酸濃度が65〜87重量%の硫酸を電気分解して、過硫酸を含む過硫酸溶液を生成する工程と、
前記生成された過硫酸溶液の温度が50〜80℃となるように加熱する工程と、
前記加熱された過硫酸溶液にABS系樹脂を5〜20分間浸漬する工程とを備え、
前記生成された過硫酸溶液の濃度が3〜20g/Lである、ABS系樹脂表面のめっき前処理方法。 - 請求項1に記載のABS系樹脂表面のめっき前処理方法により処理した後、該ABS系樹脂表面に無電解めっき又は電気めっきを施す、ABS系樹脂表面のめっき処理方法。
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JP2019154224A JP6947783B2 (ja) | 2017-09-01 | 2019-08-27 | Abs系樹脂表面のめっき前処理方法、及びabs系樹脂表面のめっき処理方法 |
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JPH01275769A (ja) * | 1988-04-28 | 1989-11-06 | Nippon Ozon Kk | 無電解メッキ素材の前処理方法 |
JP2747321B2 (ja) * | 1989-04-19 | 1998-05-06 | 日清紡績株式会社 | 金属被覆された合成樹脂製構造物の製造方法 |
WO2007122869A1 (ja) * | 2006-04-18 | 2007-11-01 | Okuno Chemical Industries Co., Ltd. | 樹脂成形体に対するエッチング処理用組成物 |
JP5403535B2 (ja) * | 2008-12-10 | 2014-01-29 | 奥野製薬工業株式会社 | エッチング液の電解処理方法 |
JP5271345B2 (ja) * | 2010-12-21 | 2013-08-21 | クロリンエンジニアズ株式会社 | 導電性ダイヤモンド電極、これを用いた、硫酸電解方法及び硫酸電解装置 |
US10260000B2 (en) * | 2012-01-23 | 2019-04-16 | Macdermid Acumen, Inc. | Etching of plastic using acidic solutions containing trivalent manganese |
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Free format text: JAPANESE INTERMEDIATE CODE: R350 |