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LT2008082A - Process for etching polyimide and other plastics - Google Patents

Process for etching polyimide and other plastics Download PDF

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Publication number
LT2008082A
LT2008082A LT2008082A LT2008082A LT2008082A LT 2008082 A LT2008082 A LT 2008082A LT 2008082 A LT2008082 A LT 2008082A LT 2008082 A LT2008082 A LT 2008082A LT 2008082 A LT2008082 A LT 2008082A
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plastics
polyimide
etching
adhesion
sulfuric acid
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LT2008082A
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Lithuanian (lt)
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Leonas NARUŠKEVIČIUS
Mykolas Baranauskas
Birutė ŠIMKŪNAITĖ-STANYNIENĖ
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Chemijos Institutas
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Abstract

The present invention relates to preparation of plastic surface for chemical metallization. It aims to simplify the process and improve the quality of polyimide and other plastic surfaces excluding use of toxic materials. The task is achieved by etching polyimide and plastics with the 0.005-0.2 M solution of oxidizers in 13-17 M sulfuric acid for 1-2 min at the temperature of 10-80 oC the oxidizers being KMnO4, HClO4, V2O5, KClO3.@

Description

11

POUIMIDO IR KITŲ PLASTIKŲ ĖSDINIMO BODAS Išradimas yra susijęs su plastikų paruošimu prieš cheminę metalizaciją,FIELD OF THE INVENTION The present invention relates to the preparation of plastics prior to chemical metallization,

Metalizuojant plastikus pirmas svarbus etapas yra plastikų ėsdinimas, Įgaliojantis gauti jų paviršiaus gerasadsorbeines ir adhezines savybes. Geros paviršiaus adsorbcines savybės garantuoja tolygų tolesnį dengimąsi metalu, adhezines - gerą mechaninį dangos sukibimą su plastiku. Ypač sunku šias savybes suteikti poliimidams.The first important step in metallizing plastics is the etching of plastics, enabling them to obtain good adsorption and adhesive properties on their surface. Good surface adsorption properties ensure even further metal coating, adhesives - good mechanical adhesion of the coating to plastic. It is especially difficult to give these properties to polyimides.

Yra žinomas poliimidų ėsdinimo būdas, apimantis apdorojimą šarminiais tirpalais bei plovimą ir ėsdinimo produktų šalinimą nuo poliimidų paviršiaus (žiūr. EP0511691, US4873136, EP0351622). Be to, prieš šarminį ėsdinimą dažnai poliimidus apdoroja įvairiomis, kartais labai kenksmingomis organinėmis medžiagomis, o tam reikalinga papildoma technologinė įranga (žiuf. EP0421123, US6218022, US2003070545, US4039371, US4112139, US6660062, US6218022).There is a known method of etching polyimides comprising treatment with alkaline solutions and washing and removal of etching products from the surface of polyimides (see EP0511691, US4873136, EP0351622). In addition, polyimides are often treated with various, sometimes very harmful, organic substances before alkaline etching, and this requires additional technological equipment (see EP0421123, US6218022, US2003070545, US 4039371, US4112139, US6660062, US6218022).

Artimiausias siOiomam išradimui yra poliimidų ėsdinimo būdas, pagal kurį poliimidus prieš šarminį ėsdinimą apdoroja organinių medžiagų tirpalais, o ėsdinimo produktus nuo paviršiaus šalina nė mažesnės negu 85% sieros rūgšties tirpalu {žiūr. US4873136). Šio būdo trūkumas yra tas, kad apima daug operaciją kurioms reikalinga sudėtinga įranga. Taip pat gautos metalo dangos sukibimas su poliimidų labai sumažėja aukštesnėje temperatūroje, Pastaroji aplinkybė yra labai svarbi, nes poliimidų plastikas skirtas naudoti padidintoje, palyginti su kitais plastikais, temperatūroje (150°G ir daugiau). Kitų plastikų sukibimą riboja ją pačių terminis atsparumas.The closest to the present invention is a method of etching polyimides, whereby the polyimides are treated with solutions of organic matter before alkaline etching, and the etching products are removed from the surface with a solution of at least 85% sulfuric acid (see Figs. US4873136). The disadvantage of this method is that it involves a lot of operation requiring complex equipment. Also, the adhesion of the resulting metal coating to the polyimide is greatly reduced at a higher temperature, the latter being very important because the polyimide plastic is intended for use in elevated temperatures compared to other plastics (150 ° G and above). The adhesion of other plastics is limited by its own thermal resistance.

Siūlomo išradimo tikslas būdo supaprastinimas bei poliimidų ir kitų plastikų paviršiaus paruošimo kokybės pagerinimas, nenaudojant toksiškų medžiagąThe aim of the proposed invention is to simplify the process and to improve the quality of surface preparation of polyimides and other plastics without the use of toxic substances.

Tiksiąs pasiekiamas tuo, kad poliimidus ir plastikus ėsdina 1-2 minutes 10 - 80°C temperatūroje, 0,005 - Q,2M oksidatorių tirpalu 13 - 17M sieros rūgštyje, o oksidatoriais gali būti KMn04l HCIO4, V205, KCi03.It will be achieved by polishing the polyimides and plastics for 1-2 minutes at 10-80 ° C, with a solution of 0.005-Q, 2M oxidants in 13-17M sulfuric acid, and the oxidizers being KMnO4l HClO4, V205, KCiO3.

Siūlomas išradimas, lyginant su artimiausiu prototipą leidžia atsisakyti 2 daugiastadijinio plastikų ėsdinimo būdo, nenaudojant toksiškų, nestabilių organinių medžiagų. Naudojamų bude neorganinių oksidatorių priedų koncentracijos yra labai mažos, tai nedidina būdo savikainos. Be to, nenaudojami kancerogeniški šešiavalenči© chromo junginiai.The proposed invention, compared to the nearest prototype, allows us to abandon 2 multi-stage etching techniques without the use of toxic, unstable organic materials. Concentrations of inorganic oxidant additives used in the body are very low, which does not increase the cost of the method. In addition, carcinogenic hexavalent chromium compounds are not used.

Siūlomame būde, poliimidą apdoroja sieros rūgštie su KMnCų priedu 20 ~ 60 °C temperatūroje 1 - Z min. Kuo didesnė sieros rūgšties koncentracija tuo mažesnės reikia temperatūros ir laiko. Naudojant 17M sieros rūgštį galima apdoroti tik kambario temperatūroje. Apdorojant aukštesnėje temperatūroje arba ilgesnį laiką - susilpnėja paviršinis poiiimido sluoksnis ir silpnėja jo sukibimas su metalu. Apdorojant 13 M sieros rūgštimi - temperatūra turi būti ne mažesnė 80°G. Dar labiau sumažinus sieros rūgšties koncentraciją negaunamas plastiko sukibimas su metalu, be to, labai sumažėja permanganato stabilumas tirpale. Esant sieros rūgšties koncentracijai 14M ir daugiau tirpalas būna aktyvus daug ilgesnį laiką net ir 60°G temperatūroje. Labai svarbi yra tirpalo permanganate jonų koncentracija. Geriausi rezultatai gauti esant 0,001 - 0,01 M koncentracijoms, kai metalo sukibimas su poliimidu siekia 1KN/m, Esant didesnei arba mažesnei negu optimali permanganato koncentracijai, žymiai sumažėja metalo dangos sukibimas su plastiku.In the proposed method, the polyimide is treated with sulfuric acid with a KMnCu additive at a temperature of 20 ~ 60 ° C 1 - Z min. The higher the sulfuric acid concentration, the lower the temperature and time required. 17M sulfuric acid can only be treated at room temperature. Treating at a higher temperature or for a longer period of time reduces the surface layer of polyimide and reduces its adhesion to the metal. When treating with 13 M sulfuric acid, the temperature should be at least 80 ° C. Further reduction of the sulfuric acid concentration does not result in plastic adhesion to the metal, and significantly reduces the stability of the permanganate in the solution. At a sulfuric acid concentration of 14M and more, the solution is active for a much longer time even at 60 ° G. The concentration of solution permanganate ions is very important. The best results are obtained at concentrations of 0.001 - 0.01 M when the metal adhesion to polyimide reaches 1KN / m, with a higher or lower than optimal concentration of permanganate, significantly reduces the adhesion of the metal coating to the plastic.

Siūlomas išradimas paaiškinamas pavyzdžiais.The proposed invention is explained by way of example.

Poiiimido plėvelę ėsdina 13 17 M su Mn04 0,0005 - 0,015 M priedu kalio, natrio arba amonio druskos pavidalu, 20 - 80 °C temperatūroje, plauna vandeniu ir aktyvuoja 1 - 2 min. kambario temperatūros tirpale, turinčiame Igll PdCI2 ir 2m|/l HCi, sensibiiizuoja 2 min 5g/i NaBH* ir 5 g/1 NaOH tirpale. Po praplovimo plėvelę dengia nikeliu 20°G temperatūros tirpale, turinčiame (gfl): NiClr10, NaH2P02 - 30, Na citrato ~ 30, NaOH - iki pH apie 10. Dengimo laikas — 5 min. Gautą cheminio nikelio dangą (tam, kad būtų galima išmatuoti dangos sukibimą su plastiku) storina žinomais elektrocheminio nikeliavimo arba variavimo būdais. Metelė sukibimo su plastiku Įvertinimui matuoja jėgą, reikalingąatplėštl 1 cm dangos pločio juostelę. Matuoja šviežiai 3 gautos dangos sukibimą su polfimidu ir po 7 parą kaitinimo 150°G temperatūroje.The polyimide film is etched in 13 17 M with Mn04 0.0005 - 0.015 M additive in the form of potassium, sodium or ammonium salt at 20 - 80 ° C, washed with water and activated for 1 - 2 min. in a room temperature solution containing Igll PdCl2 and 2mL HCl, sensitizes 2 min in 5 g / l NaBH * and 5 g / l NaOH solution. After flushing, the film is coated with nickel in a solution of (gfl) at 20 ° C: NiClr10, NaH2P02 - 30, Na citrate ~ 30, NaOH - to a pH of about 10. Coating time - 5 min. The resulting chemical nickel coating (in order to measure the adhesion of the coating to plastics) is thickened by known electrochemical nickel plating or varnishing techniques. MELELY FOR PLATING WITH PLASTIC MATERIAL MEASURES THE STRENGTH REQUIRED TO RUN 1 cm Tape Width. Measures the adhesion of freshly obtained 3 coatings to polyphimide and after 7 days heating at 150 ° C.

Rezultatai pateikti 1 lentelėje 1 lentelėTable 1 shows the results

Pavyzdys HaSCį koncentra cija (mol/i) UnOĄ koncentra cija {moi/i> Esdinimo stygos Dangos sukibimas su poliimidu (kN/m) Tempe ratūra °C laite (min) Šviežios Po iškaiti-nimo (150°D, 7 paros) 1 14. 0,005 20 2 1 0,8 ,2 15 0,005 20 1 0,9 0,7 3 14 0,005 60 1 0,9 0,8 4 13 0,005 60 2 0,8 0,6 5 17 0,005 20 1 0,7 0,5 6 14 0,0005 60 2 0,2 0,1 7 14 0,05 60 2 0,2 0,1 8 14 0,005 20 5 0,4 0,3 9 16 0,005 20 1 0,9 0,7 10 16 0 20 2 0 0 11 16 0 60 10 0 0 12 14 0,005 20 0,5 .0,5 0,4 Iš 1 lentelės matyti, kad naudojant poliimido ėsdinimui 13 - 17M sieros rugštį su 0,005 M permanganato priedu, gaunamas geras metalo dangos sukibimas su pollimidu (žiur. t — S Ir 9 pavyzdžius). Sukibimas termiškai stabilus. Naudojant ėsdinimui sieros rūgštį be permanganato priedo, sukibimas 4 negaunamas, nepriklausomai nuo ėsdinimo sąlygų (žiūr, 10 ir 11 pavyzdžius}. Padidinus arba sumažinus permanganato fonų koncentraciją, sukibimas mažėja (6 ir 7 pavyzdžiai. Iš B pavyzdžio matyti, kad nei ir esant optimalioms sieros rūgšties ir permanganato koncentracijoms, ilgesnis ėsdinimas blogina sukibimą. Sumažinus ėsdinimo laiką - sukibimas irgi sumažėja. Todėl optimaliomis poliimido ėsdinimo sąlygomis galima laikyti 1 ~ 2 min 20 « 60°C temperatūroje, esant sieros koncentracijai 13 - 17M ir permanganato koncentracijai apie 0,O6§M.Example HaSC Concentration (mol / i) Uno concentration {moi / i > Adjustment straps Adhesion of the coating to polyimide (kN / m) Temperature ° C device (min) Fresh After cutting (150 ° D, 7 days) 1 14. 0.005 20 2 1 0.8, 2 15 0.005 20 1 0, 9 0,7 3 14 0,005 60 1 0,9 0,8 4 13 0,005 60 2 0,8 0,6 5 17 0,005 20 1 0,7 0,5 6 14 0,0005 60 2 0,2 0,1 7 14 0.05 60 2 0.2 0.1 8 14 0.005 20 5 0.4 0.3 9 16 0.005 20 1 0.9 0.7 10 16 0 20 2 0 0 11 16 0 60 10 0 0 12 14 0.005 20 0.5 .0.5 0.4 Table 1 shows that using a 13-17M sulfur spring with a 0.005 M permanganate additive for polyimide etching, a good adhesion of the metal coating to pollimide (j - t - S and 9 samples) is obtained . The adhesion is thermally stable. When using sulfuric acid for etching without the addition of permanganate, adhesion 4 is not obtained, irrespective of the etching conditions (see examples 10 and 11). Increasing or decreasing the permanganate background concentration reduces adhesion (Examples 6 and 7. Example B shows that both are optimal By reducing the etching time, adhesion is also reduced, therefore, under optimal polyimide etching conditions, it can be stored at 1 ~ 2 min at 20 60 60 ° C, with a sulfur concentration of 13-17M and a permanganate concentration of about 0, O6. §M.

Siūlomą būdą galime naudoti ir kitų plastikų ėsdinimui, be to kaip priedus į sieros rūgštį be permanganato, naudoja ir kitus oksidatorius (žiūr. 2 lentelę) 2 lentelėWe can also use the proposed method for etching other plastics, as well as using other oxidants as additives in sulfuric acid without permanganate (see Table 2).

Pavy zdys h2so4 konc entra cija (mol/i) Oksidatoriaus priedas į sieros rūgštį Plas, tikas Ėsdinimo sąlygos Dangos sukibimas su plastiku (kN/m) Oksida torius (mol/I) Tempe-ratūra °C baikas (min) 13 14 ΚΜηθ4 0,005 ABS 20 1 1,4 14 15 KMn04 0,005 ABS-PC 20 2 0,7 15 16 HCI04 0,1 ABS 20 1 0,7 16 7 W>5 0,1 SP 80 2 0,4 17 7 KCIO3 0,2 ABS 30 2 0,9 ABS - Aknionitrilo ir butadienstirolo kopolimeras ABS - PC - Aknionitrilo ir butadienstirolo kopolimeras su polikarbonatu SP “ stiklo plastikas epoksidinės dervos pagrinduExample h2so4 Concentration (mol / i) Sulfuric acid additive Plas, Teas Pickling conditions Coating with plastics (kN / m) Oxidation thorium (mol / I) Tempeurate ° C ramp (min) 13 14 ΚΜηθ4 0.005 ABS 20 1 1.4 14 15 KMn04 0.005 ABS-PC 20 2 0.7 15 16 HClO 0.1 ABS 20 1 0.7 16 7 W > 5 0.1 SP 80 2 0.4 17 7 KCIO3 0.2 ABS 30 2 0.9 ABS - Copolymer of acrylonitrile and butadiene styrene ABS - PC - Copolymer of acrylonitrile and butadiene styrene with polycarbonate SP "glass plastic based on epoxy resin

Claims (2)

iSradimo apibrėžtis 1. Poliimido ir kitų plastikų ėsdinimo būdas, apimantis poiiimidų ir kitų plastiką apdorojimą H2S04, besiskiriantis tuo, kad poliiimldą ar kitą plastiką ėsdina 1-2 minutes 10 - 8Q°C temperatūroje, 0,005 ~ 0,2M oksidatorių tirpalu 13 -17 M sieros rūgštyje.Definition of the invention 1. A method of etching polyimide and other plastics, comprising polyimide and other plastics treatment with H2SO4, characterized in that the polyimide or other plastic is etched for 1-2 minutes at 10-8 ° C, with a 0.005-2.2M oxidant solution 13 -17M. sulfuric acid. 2. Būdas pagal apibrėžties 1 punktą, b e s i s k i r i a n t i s tuo, kad oksidatorių tirpalai yra KMn04, HCIO4, V205, KCIO3.Process according to claim 1, characterized in that the oxidizing agent solutions are KMnO 4, HCl 4, V 2 O 5, KCl 3.
LT2008082A 2008-10-28 2008-10-28 Process for etching polyimide and other plastics LT2008082A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013182590A1 (en) 2012-06-05 2013-12-12 Atotech Deutschland Gmbh Process for metallizing nonconductive plastic surfaces
WO2014087004A1 (en) 2012-12-07 2014-06-12 Atotech Deutschland Gmbh Process for metallizing nonconductive plastic surfaces
EP2767614A1 (en) * 2013-02-13 2014-08-20 ATOTECH Deutschland GmbH Method for depositing a first metallic layer onto non-conductive polymers

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013182590A1 (en) 2012-06-05 2013-12-12 Atotech Deutschland Gmbh Process for metallizing nonconductive plastic surfaces
CN104364421A (en) * 2012-06-05 2015-02-18 安美特德国有限公司 Process for metallizing nonconductive plastic surfaces
KR20150024327A (en) * 2012-06-05 2015-03-06 아토테크더치랜드게엠베하 Process for metallizing nonconductive plastic surfaces
CN104364421B (en) * 2012-06-05 2017-07-21 安美特德国有限公司 Method for metallizing non-conductive plastic surfaces
KR102130947B1 (en) 2012-06-05 2020-07-08 아토테크더치랜드게엠베하 Process for metallizing nonconductive plastic surfaces
WO2014087004A1 (en) 2012-12-07 2014-06-12 Atotech Deutschland Gmbh Process for metallizing nonconductive plastic surfaces
CN104854216A (en) * 2012-12-07 2015-08-19 埃托特克德国有限公司 Process for metallizing nonconductive plastic surfaces
EP2767614A1 (en) * 2013-02-13 2014-08-20 ATOTECH Deutschland GmbH Method for depositing a first metallic layer onto non-conductive polymers
WO2014124773A3 (en) * 2013-02-13 2014-12-31 Atotech Deutschland Gmbh Method for depositing a first metallic layer onto non-conductive polymers
CN104995335A (en) * 2013-02-13 2015-10-21 埃托特克德国有限公司 Method for depositing a first metallic layer onto non-conductive polymers

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