LT6070B - Plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas - Google Patents

Plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas Download PDF

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LT6070B
LT6070B LT2012110A LT2012110A LT6070B LT 6070 B LT6070 B LT 6070B LT 2012110 A LT2012110 A LT 2012110A LT 2012110 A LT2012110 A LT 2012110A LT 6070 B LT6070 B LT 6070B
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solution
etching
chemical metallization
plastic surface
plastics
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LT2012110A
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LT2012110A (lt
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Leonas NARUŠKEVIČIUS
Danas Budilovskis
Ona GYLIENĖ
TAMAŠIŪNAITĖ Loreta TAMAŠAUSKAITĖ
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Atotech Deutschland Gmbh
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Priority to LT2012110A priority Critical patent/LT6070B/lt
Priority to KR1020177009056A priority patent/KR20170039775A/ko
Priority to KR1020157018064A priority patent/KR20150093214A/ko
Priority to EP13799621.1A priority patent/EP2928984A1/en
Priority to US14/647,499 priority patent/US20150307992A1/en
Priority to BR112015012930A priority patent/BR112015012930A2/pt
Priority to JP2015546043A priority patent/JP2015537122A/ja
Priority to PCT/EP2013/075863 priority patent/WO2014087004A1/en
Priority to CN201380063675.4A priority patent/CN104854216A/zh
Priority to CA2893664A priority patent/CA2893664C/en
Publication of LT2012110A publication Critical patent/LT2012110A/lt
Publication of LT6070B publication Critical patent/LT6070B/lt

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Abstract

Išradimas priskiriamas prie plastikų paviršiaus paruošimo prieš cheminį metalizavimą ir gali būti panaudotas įvairiose pramonės srityse, kur reikalingos dekoratyvinės arba funkcinės metalų dangos ant plastikų. Siūlomo išradimo tikslas yra kokybiškas plastikų paviršiaus paruošimas prieš cheminį metalizavimą, naudojant karštą chloratinį ėsdinimo tirpalą, ir tuo išsaugant aukštas nikelio dangos sukibimo su plastiku reikšmes. Tikslas pasiekiamas tuo, kad plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas, apimantis paviršiaus ėsdinimą chlorato jonų ir papildomo oksidatoriaus turinčiame sieros rūgšties tirpale ir po jo sekantį apdorojimą šarminio metalo hidroksidų turinčiame tirpale, aktyvavimą paladžio druskos tirpale bei apdorojimą redukuojančiame arba akceleruojančiame tirpale, papildomai į ėsdinimo tirpalą įveda 0,1-8 g/l vanadžio junginio, o ėsdinimą atlieka 20-65 oC temperatūroje.

Description

Išradimas priskiriamas prie plastikų paviršiaus paruošimo prieš cheminį metalizavimą ir gali būti panaudotas įvairiose pramones srityse, kur reikalingos dekoratyvinės arba funkcinės metalų dangos ant plastikinių detalių.
Tradicinį plastikų paviršiaus paruošimo prieš cheminį metalizavimą būdą, dažniausiai cheminį nikeliavimą, sudaro ėsdinimas chromo rūgšties tirpale, po to sekantis aktyvinimas paladžio junginių joniniame arba koloidiniame tirpale ir adsorbuotų ant plastiko paviršiaus paladžio jonų arba paladžio koloidinių dalelių atitinkamai redukavimas dažniausiai natrio hipofosfito tirpale arba akceleracija rūgščiame, dažniausiai druskos rūgšties, tirpale.
Ėsdinimas reikalingas suteikti paviršiui hidrofiliškumą, kad kitose proceso stadijose jis drėkintųsi vandeniniais tirpalais, adsorbuodamas pakankamus paladžio druskų kiekius, ir užtikrinti gerą metalo dangos sukibimą su plastiku. Aktyvavimas su po to sekančiu redukavimu arba akceleracija atliekamas tam, kad inicijuoti cheminio metalo nusėdimo ant plastiko pradžią. Po to dengimasis metalu cheminio metalizavimo tirpale jau vyksta autokatalitiškai, t.y. išsėdęs iš tirpalo metalas katalizuoja tolimesnį metalo nusėdimą.
Pagrindiniai tradicinio būdo trūkumai yra chromo rūgšties ėsdinimo tirpale kancerogeniškumas bei dažnai pasitaikantis cheminis metalo, dažniausiai nikelio, nusėdimas ant izoliuotų plastizoliu pakabos dalių, dėl ko patiriami metalų nuostoliai toliau sekančio galvaninio dangos formavimo tirpaluose. Artimiausias siūlomam išradimui yra plastikų paviršiaus paruošimo būdas (žiūr. LR išradimo paraiška 2012 042, padavimo data 2012-06-05), apimantis plastiko ėsdinimą kambario temperatūros 0,5-5 g/l tirpaus chlorato tirpale 50-80 tūrio % sieros rūgštyje ir po to sekantį apdorojimą šarminių metalų hidroksidų tirpale. Ėsdinimo tirpalas papildomai turi, be chlorato, kito oksidatoriaus, kurio standartinis oksidacinis potencialas viršija chlorato jonų potencialą. Po apdorojimo šarminių metalų hidroksidų tirpale plastikas aktyvuojamas paladžio junginių tirpale, toliau išlaikomas redukuojančiame arba akseleruojančiame tirpale ir nikeliuojamas cheminio nikeliavimo tirpale. Būdo teigiami bruožai yra didelės nikelio dangos su plastiku sukibimo reikšmės ir tai, kad plastizoliu padengta plastikų detalizavimo įranga išlieka nepasidengusi nikelio danga.
Būdo trūkumas - ėsdinimo tirpalo savybė absorbuoti iš aplinkos oro vandens garus ir tokiu būdu prasiskiedžiant, praranda efektyvaus ėsdinimo savybes. Šios problemos sprendimas būtų ėsdinimo tirpalo temperatūros didinimas iki lygio, kai oro drėgmės absorbciją kompensuoja vandens garavimas iš tirpalo. Tačiau tais atvejais, kai ėsdinimo tirpalo temperatūra viršija 30 °C, gaunamos nikelio dangos sukibimo su plastiku reikšmės yra žymiai mažesnės ir netgi gali kristi iki nulio.
Siūlomo išradimo tikslas yra kokybiškas plastikų paviršiaus paruošimas prieš cheminį metalizavimą, naudojant karštą chloratinj ėsdinimo tirpalą, ir tuo išsaugant aukštas nikelio dangos sukibimo su plastiku reikšmes.
Tikslas pasiekiamas tuo, kad plastikų paviršiaus paruošimo prieš jų cheminj metalizavimą būdas, apimantis paviršiaus ėsdinimą chlorato jonų ir papildomo oksidatoriaus turinčiame sieros rūgšties tirpale ir po jo sekantį apdorojimą šarminio metalo hidroksidų turinčiame tirpale, aktyvavimą paladžio druskos tirpale bei apdorojimą redukuojančiame arba akceleruojančiame tirpale, papildomai į ėsdinimo tirpalą įveda 0,1-8 g/l vanadžio junginio, o ėsdinimą atlieka 20-65 °C temperatūroje.
Įeinantis j ėsdinimo tirpalo sudėtj vanadžio junginys dalyvauja plastiko ėsdinimo procese tiek kaip papildomas plastiko paviršių oksiduojantis agentas, tiek kaip katalizatorius chlorato jonų oksiduojamajam veikimui. Turintį vanadžio junginio ėsdinimo tirpalą naudoja esant 20-65 °C temperatūrai, o gaunamų ant plastiko nikelio dangų adhezijos reikšmės yra ne žemesnės, negu prototipo. Be to, toks tirpalas, naudojant jį aukštesnės temperatūros, gali būti labiau praskiestas sieros rūgšties atžvilgiu ir todėl pigesnis ir saugesnis darbe.
Svarbus siūlomo būdo bruožas, besiskiriantis nuo prototipo, yra galimybė efektyviau ėsdinti liedinimo alyvomis užterštus plastikų paviršius, kadangi aukštoje temperatūroje liedinimo alyvas chemiškai suardo (oksiduoja) ėsdinimo tirpalo komponentai ir alyvos nebetrukdo ėsdinimo procesui.
Pavyzdžiai
Plastikus ABS (akrilo-nitril-butadien-stirolo kopolimeras) ir PC/ABS (55 % akrilo-nitril-butadien-stirolo kopolimero ir 45 % polikarbonato mišinys) ėsdina 5 min 120 g/l KCIO3 ir 10 g/l papildomo oksidatoriaus KJO4 turinčioje 30-70 tūrio % sieros rūgštyje 20 °C, 40 °C ir 65 °C temperatūroje arba ėsdina tokios pat kompozicijos tirpale tomis pat sąlygomis, tačiau į tirpalą papildomai įvedus 0,1-10 g/l tirpaus vanadžio junginio. Po ėsdinimo plastikus pamerkia 2 min. j kambario temperatūros neutralizavimo tirpalą, turintį 10 g/l NaOH ir toliau aktyvuoja tikrajame (5 min esant 20 °C temperatūrai) paladžio junginių tirpale. Tikrajame tirpale PdCI2 koncentracija yra 0,1 g/l, tirpalo pH 2,7. Po aktyvacijos tikrajame Pd tirpale plastikus išlaiko 5 min, esant 60 °C temperatūrai bei turinčiame 20 g/l natrio hipofosfito, pH 9. Po to plastikus dengia cheminiu nikeliu pagal kompanijos D0W Chemicals technologiją NipositPM. Dengimosi kokybę vertina pagal dangos sukibimo su plastiku stiprumą (adheziją). Adhezijai įvertinti Ni dangos sluoksnis storinamas galvaninėje variavimo vonioje ir matuojama jėga, reikalinga atplėšti 1 cm pločio dangos juostelei nuo plastiko (kg/cm). Plastikų paruošimo metalizacijai sąlygos ir metalizacijos (cheminio nikeliavimo) rezultatai pateikti Lentelėje.
Iš pateiktų 1 ir 2 pavyzdžių matosi, kad ėsdinimo tirpalas, neturintis savo sudėtyje vanadžio junginių, ABS plastiko ėsdinimui gali būti naudojamas tik kambario temperatūroje. Esant aukštesnei ėsdinimo tirpalo temperatūrai, pavyzdžiui 40 oC, gaunamų ant ABS Ni dangų adhezija yra artima nuliui. Tuo atveju, jeigu ėsdinimo tirpale yra vanadžio junginio (3 ir 4 pavyzdžiai) Ni dangos adhezija su ABS ėsdinant aukštesnės temperatūros tirpale yra ne mažesnė negu nesant tirpale vanadžio junginio ir ėsdinant kambario temperatūroje. Iš pateiktų 5, 6 ir 7 pavyzdžių matosi, kad tie patys dėsningumai esant arba nesant ėsdinimo tirpale vanadžio junginio, pasireiškia ir ėsdinant PC/ABS plastiką. Iš 8, 9, 10 ir 11 pavyzdžių duomenų matosi, kad sieros rūgšties koncentracija ėsdinimo tirpale gali būti sumažinta iki 30 tūrio %, jeigu ėsdinama 65 °C temperatūroje. Tačiau sieros rūgšties koncentraciją mažinti labiau negu iki 30 tūrio % neverta, nes Ni dangos adhezija ant plastikų, net ir esant 30 tūrio %, pastebimai mažesnė. 12 ir 13 pavyzdžiai liudija, kad vanadžio junginio koncentraciją ėsdinimo tirpale mažinti labiau negu 0,1 g/l arba didinti labiau negu 8 g/l netikslinga, nes gaunamos pastebimai mažesnės Ni dangos adhezijos reikšmės.
Visų 13 pavyzdžių atveju plastiko pavyzdžiai Ni danga pasidengė pilnai, o Ni danga ant plastizolinių įrangos dalių nesiformavo.
Lentelė
Pvz. Nr. Plastikas H2SO4 koncentra cija ėsdinimo tirpale, tūrio % KCIO3 koncentra cija ėsdinimo tirpale, tūrio % Ėsdinimo temperai ura,°C Vanadžio junginys ir jo koncentracija ėsdinimo tirpale, g/l Gautos adhezijos reikšmės, kg/cm
1 ABS 66 2 20 - 1,0-1,3
2 ABS 66 2 40 - 0-0,1
3 ABS 66 2 40 V2O5, 0,5 1,1-1,3
4 ABS 66 2 65 V2O5, 0,5 1,3-1,4
5 PC/ABS 66 2 20 - 0,7-0,9
6 PC/ABS 66 2 65 - 0-0,1
7 PC/ABS 66 2 65 V2O5, 0,5 0,9-1,1
8 ABS 40 10 65 NaVO3, 1,0 1,0-1,2
9 PC/ABS 40 10 65 NaVO3, 1,0 0,7-0,9
10 ABS 30 10 65 NaVO3, 1,0 0,5-0,7
11 PC/ABS 30 10 65 NaVO3, 1,0 0,3-0,5
12 ABS 66 2 65 V2O5, 0,1 1,0-1,3
13 ABS 66 2 65 V2O5, 8,0 0,8-1,0

Claims (1)

  1. IŠRADIMO APIBRĖŽTIS
    Plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas, apimantis paviršiaus ėsdinimą chlorato jonų ir papildomo oksidatoriaus turinčiame sieros rūgšties tirpale ir po jo sekantį apdorojimą šarminio metalo hidroksidų turinčiame tirpale, aktyvavimą paladžio druskos tirpale bei apdorojimą redukuojančiame arba akceleruojančiame tirpale, besiskiriantis tuo, kad į ėsdinimo tirpalą papildomai įveda 0,1-8 g/l vanadžio junginio, o ėsdinimą atlieka 2065 °C temperatūroje.
LT2012110A 2012-12-07 2012-12-07 Plastikų paviršiaus paruošimo prieš jų cheminį metalizavimą būdas LT6070B (lt)

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KR1020177009056A KR20170039775A (ko) 2012-12-07 2013-12-06 비전도성 플라스틱 표면들을 금속화하기 위한 방법
KR1020157018064A KR20150093214A (ko) 2012-12-07 2013-12-06 비전도성 플라스틱 표면들을 금속화하기 위한 프로세스
EP13799621.1A EP2928984A1 (en) 2012-12-07 2013-12-06 Process for metallizing nonconductive plastic surfaces
US14/647,499 US20150307992A1 (en) 2012-12-07 2013-12-06 Process for metallizing nonconductive plastic surfaces
BR112015012930A BR112015012930A2 (pt) 2012-12-07 2013-12-06 processo para a metalização de superfícies plásticas não condutoras
JP2015546043A JP2015537122A (ja) 2012-12-07 2013-12-06 非導電性プラスチック表面の金属化方法
PCT/EP2013/075863 WO2014087004A1 (en) 2012-12-07 2013-12-06 Process for metallizing nonconductive plastic surfaces
CN201380063675.4A CN104854216A (zh) 2012-12-07 2013-12-06 用于对绝缘塑料表面进行金属化的方法
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