JP2019203203A - Abs系樹脂表面のめっき前処理方法、abs系樹脂表面のめっき処理方法、及びabs系樹脂めっき製品 - Google Patents
Abs系樹脂表面のめっき前処理方法、abs系樹脂表面のめっき処理方法、及びabs系樹脂めっき製品 Download PDFInfo
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- JP2019203203A JP2019203203A JP2019153409A JP2019153409A JP2019203203A JP 2019203203 A JP2019203203 A JP 2019203203A JP 2019153409 A JP2019153409 A JP 2019153409A JP 2019153409 A JP2019153409 A JP 2019153409A JP 2019203203 A JP2019203203 A JP 2019203203A
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 92
- 238000007747 plating Methods 0.000 title claims abstract description 85
- 238000002203 pretreatment Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 34
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 75
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 claims description 39
- 238000007772 electroless plating Methods 0.000 claims description 11
- 238000009713 electroplating Methods 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 11
- 229910052804 chromium Inorganic materials 0.000 abstract description 8
- 229910003460 diamond Inorganic materials 0.000 abstract description 3
- 239000010432 diamond Substances 0.000 abstract description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 abstract description 3
- 235000011149 sulphuric acid Nutrition 0.000 abstract 2
- 239000001117 sulphuric acid Substances 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 40
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 238000012545 processing Methods 0.000 description 24
- 239000004094 surface-active agent Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000011651 chromium Substances 0.000 description 12
- 230000004913 activation Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 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
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000004417 polycarbonate Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 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
- 238000010306 acid treatment Methods 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- -1 specifically Polymers 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing 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
- 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
- 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
- 239000011630 iodine Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000007781 pre-processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052718 tin Inorganic materials 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
- 230000003213 activating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 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
- 230000015572 biosynthetic process Effects 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
- 239000000084 colloidal system Substances 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
- 230000007423 decrease Effects 0.000 description 1
- 238000007598 dipping method 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
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 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
- 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
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 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
- 239000011135 tin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Abstract
Description
2CrO4 2−+2H3O+→Cr2O7 2−+3H2O
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 (6)
- ABS系樹脂を硫酸を電気分解した溶液で処理する、ABS系樹脂表面のめっき前処理方法。
- 前記溶液の硫酸濃度が60〜87重量%である、請求項1に記載のABS系樹脂表面のめっき前処理方法。
- 前記処理の温度が50〜80℃である、請求項1又は2に記載のABS系樹脂表面のめっき前処理方法。
- 前記溶液の過硫酸濃度が3g/L以上である、請求項1〜3のいずれかに記載のABS系樹脂表面のめっき前処理方法。
- 請求項1〜4のいずれかに記載の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。
- 請求項5に記載のABS系樹脂表面のめっき処理方法によりめっき処理を施した、ABS系樹脂めっき製品。
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JP2019153409A JP6953484B2 (ja) | 2017-09-01 | 2019-08-26 | Abs系樹脂表面のめっき前処理方法、abs系樹脂表面のめっき処理方法、及びabs系樹脂めっき製品 |
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JP2010138434A (ja) * | 2008-12-10 | 2010-06-24 | Okuno Chem Ind Co Ltd | エッチング液の電解処理方法 |
JP2010535935A (ja) * | 2007-08-10 | 2010-11-25 | エントン インコーポレイテッド | プラスチック表面のための無クロム酸洗 |
JP2012132066A (ja) * | 2010-12-21 | 2012-07-12 | Chlorine Engineers Corp Ltd | 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 |
JP2015518083A (ja) * | 2012-01-23 | 2015-06-25 | マクダーミッド アキューメン インコーポレーテッド | 三価マンガンを含む酸性溶液を用いたプラスチックのエッチング |
JP2017101304A (ja) * | 2015-12-04 | 2017-06-08 | 株式会社Jcu | 樹脂表面のエッチング方法およびこれを利用した樹脂へのめっき方法 |
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JP2010535935A (ja) * | 2007-08-10 | 2010-11-25 | エントン インコーポレイテッド | プラスチック表面のための無クロム酸洗 |
JP2010138434A (ja) * | 2008-12-10 | 2010-06-24 | Okuno Chem Ind Co Ltd | エッチング液の電解処理方法 |
JP2012132066A (ja) * | 2010-12-21 | 2012-07-12 | Chlorine Engineers Corp Ltd | 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 |
JP2015518083A (ja) * | 2012-01-23 | 2015-06-25 | マクダーミッド アキューメン インコーポレーテッド | 三価マンガンを含む酸性溶液を用いたプラスチックのエッチング |
JP2017101304A (ja) * | 2015-12-04 | 2017-06-08 | 株式会社Jcu | 樹脂表面のエッチング方法およびこれを利用した樹脂へのめっき方法 |
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