CN103966582B - The chemical bronze plating liquid of copper coating and using method for Kapton - Google Patents
The chemical bronze plating liquid of copper coating and using method for Kapton Download PDFInfo
- Publication number
- CN103966582B CN103966582B CN201410137110.2A CN201410137110A CN103966582B CN 103966582 B CN103966582 B CN 103966582B CN 201410137110 A CN201410137110 A CN 201410137110A CN 103966582 B CN103966582 B CN 103966582B
- Authority
- CN
- China
- Prior art keywords
- plating liquid
- chemical bronze
- bronze plating
- kapton
- sodium
- 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.)
- Expired - Fee Related
Links
- 238000007747 plating Methods 0.000 title claims abstract description 91
- 239000000126 substance Substances 0.000 title claims abstract description 65
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 48
- 239000010974 bronze Substances 0.000 title claims abstract description 48
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000007788 liquid Substances 0.000 title claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 33
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims abstract description 13
- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 claims abstract description 13
- 229940074446 sodium potassium tartrate tetrahydrate Drugs 0.000 claims abstract description 13
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 12
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 12
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000003381 stabilizer Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000002360 preparation method Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 229960004756 ethanol Drugs 0.000 claims description 12
- 229920001721 polyimide Polymers 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 9
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 8
- -1 and reflux 3h Chemical compound 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims description 4
- 238000001953 recrystallisation Methods 0.000 claims description 4
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- GODZNYBQGNSJJN-UHFFFAOYSA-N 1-aminoethane-1,2-diol Chemical compound NC(O)CO GODZNYBQGNSJJN-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002932 luster Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 208000037656 Respiratory Sounds Diseases 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
The invention provides the chemical bronze plating liquid of a kind of copper coating for Kapton and using method, its raw material includes mantoquita 10g/L～20g/L, stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 1g/L～3g/L, sodium ethylene diamine tetracetate chelating agent 30g/L～50g/L, hydramine 10g/L～20g/L, Gemini type quaternary ammonium salt 3g/L～5g/L, sodium potassium tartrate tetrahydrate 5g/L～8g/L, dodecylbenzene sodium sulfonate 0.5g/L～1.5g/L, sodium hypophosphite 4g/L～10g/L, adds deionized water to 1L。This chemical bronze plating liquid is stable, quality of coating good, environmental pollution is little。
Description
Technical field
The present invention relates to flexible printing technical field, particularly relate to a kind of chemical bronze plating liquid for Kapton copper coating and using method。
Background technology
Flexible printed-circuit board (FPC) and the rigid-flexible many uses of combined circuit plate have polyimide base material, polyimide material to have the hot property of excellence, mechanical performance and electrical property。But simultaneously because polyimide surface unusual light, in the chemical-copper-plating process process of printed circuit board Making programme, need polyimide base material resin surface is suitably processed, the roughness of resin surface and hydrophilic ability could be strengthened, ensure the adhesion of chemical plating copper layer and base material, it is to avoid chemical plating copper layer peels off and causes hole metallization to lose efficacy。For multilayer circuit board, it is also possible to the dirt stayed after removing boring by this technique。The effect of desmearing is to remove the resin melten gel (especially the melten gel on internal layer copper ring) produced in high-speed drilling process because of high temperature, it is ensured that the height reliability that electroless copper rear board internal layer copper is connected with outer circuit。
In Manufacturing Technology for PCB, most critical is exactly electroless copper operation。Its main effect makes two-sided and multilayer printed circuit board nonmetal hole exactly, deposits one layer of uniform conductive layer by redox reaction, thicken copper facing then through plating, reach the purpose in loop on hole wall。Reach this purpose to be necessary for selecting stable performance, reliable chemical pretreatment solution and formulating correct, feasible and effective process。
Along with the development of integrated circuit, electroless copper technology develops to pollution-freeization direction。But traditional chemical-copper-plating process, with formaldehyde for reducing agent, EDTA and sodium potassium tartrate tetrahydrate are individually or mixed twine mixture, wherein, the formaldehyde adopted, environmental pollution is serious, and its smell is awful, there is teratogenecity, mutagenicity, carcinogenecity。And alkaline copper plating bath can change the structure of Kapton, make its surface modification, therefore the electroless copper of polyimide surface it is not suitable for, therefore, for this problem, have been developed for some formaldehydeless chemical copper plating solutions, but, the formaldehydeless chemical copper plating solution of most conventional, due to their high response, has poor stability, and quickly decomposes when using。It is thus desirable to exploitation has the formaldehydeless chemical plating fluid of high stability, and use it can be quickly completed electroless copper process。
Additionally, using dimethyamine borane as the acidity of reducing agent and neutral chemical copper plating bath, though this copper plating bath is applicable to Kapton, but DMAB expensive and also poisonous, the borate obtained discharges has negative effect to environment。Therefore, the development of integrated circuit need nonetheless remain for environmental protection, suitable in the neutral chemical copper plating bath of Kapton。
Summary of the invention
The present invention is directed to chemical bronze plating liquid of the prior art and be not suitable for that chemical plating polyimide film surface copper, environmental pollution be big, the shortcoming of poor stability, the present invention provides a kind of chemical bronze plating liquid for Kapton copper coating, and it is stable, quality of coating is good, environmental pollution is little。
For solving above-mentioned technical problem, the invention provides a kind of chemical bronze plating liquid for Kapton copper coating, its raw material includes mantoquita 10g/L～20g/L, stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 1g/L～3g/L, sodium ethylene diamine tetracetate chelating agent 30g/L～50g/L, hydramine 10g/L～20g/L, Gemini type quaternary ammonium salt 3g/L～5g/L, sodium potassium tartrate tetrahydrate 5g/L～8g/L, dodecylbenzene sodium sulfonate 0.5g/L～1.5g/L, sodium hypophosphite 4g/L～10g/L, add deionized water in the feed, the chemical bronze plating liquid being made into 1L is a。
Preferred: described raw material includes mantoquita 15g/L, stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 2g/L, sodium ethylene diamine tetracetate chelating agent 40g/L, hydramine 15g/L, Gemini type quaternary ammonium salt 4g/L, sodium potassium tartrate tetrahydrate 6g/L, dodecylbenzene sodium sulfonate 1g/L, sodium hypophosphite 8g/L, adding deionized water in the feed, the chemical bronze plating liquid being made into 1L is a。
Wherein, the pH value of described chemical bronze plating liquid is 11～12。
Wherein, described mantoquita can be one or more mixing in copper nitrate, copper sulfate, copper chloride。
Wherein, described hydramine to be carbon number be 2～6 a hydramine or glycol amine。
Wherein, described 5-methyl-4-(preparation method of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole includes:
The first step, takes 2.93g (0.01mol) 6-methoxyl group-2-(2-bromine propiono) naphthalene, 30mL ethanol, 0.76g (0.01mol) thiourea, and reflux 3h, and ammonia adjusts pH value to be 8～9, and stirring is filtered, and dries to obtain light yellow solid；
Second step, the salicylide of 1mmol is dissolved in 5mL dehydrated alcohol, the ethanol solution that be slowly added dropwise prepared by 1mmol first step light yellow solid is stirred at room temperature down, finish, backflow 4h, cooling, sucking filtration, dehydrated alcohol recrystallization, obtains 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole。
Wherein, the preparation method of described Gemini type quaternary ammonium salt includes:
The first step, adds 13.4g Disodium oxalate., 25.0g epoxychloropropane and 100ml dehydrated alcohol in 250ml there-necked flask, reacts 10h in 50 DEG C under agitation, after having reacted, reaction system is down to room temperature, filter, remove the sodium chloride that reaction generates。By filtrate as 24h in-20 DEG C of refrigerator-freezers, crystallization, filter, filter cake obtains intermediate as 24h dry in 50 DEG C of vacuum drying ovens after using-20 DEG C of ethanol rinse 3 times；
Second step, adds intermediate prepared by the 10.1g first step, 24.9g dodecyl-dimethyl amine hydrochlorate and 100ml dehydrated alcohol in 250ml there-necked flask, reacts 10h in 50 DEG C under agitation。After having reacted, reaction system is down to room temperature, filters, remove the sodium chloride that reaction generates, by filtrate as 24h in-20 DEG C of refrigerator-freezers, crystallization, filter, filter cake use less than after 5 DEG C of distilled water drip washing 3 times as 24h dry in 50 DEG C of vacuum drying ovens。Weigh to obtain Gemini quaternary surfactant。
Present invention also offers the using method of above-mentioned chemical copper plating solution, particularly as follows:
Above-mentioned chemical copper plating solution is warming up to 40 DEG C, with nitrogen to bubbling in this chemical bronze plating liquid, treated Kapton is soaked 4 hours in above-mentioned chemical bronze plating liquid；Kapton is taken out, with deionized water rinsing 1 minute, then adopts nitrogen air blast 4 minutes, obtain polyimides plating piece。
Beneficial effects of the present invention:
The present invention provides a kind of novel chemical bronze plating liquid for Kapton, and it is stable, quality of coating is good, environmental pollution is little。
Accompanying drawing illustrates:
Fig. 1 is the characteristic absorption group infrared spectrum of Gemini quaternary surfactant；
Fig. 2 is 5-methyl-4-(the 1HNMR collection of illustrative plates of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole。
Detailed description of the invention
The invention provides the chemical bronze plating liquid of a kind of copper coating for Kapton, its raw material includes mantoquita 10g/L～20g/L, stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 1g/L～3g/L, sodium ethylene diamine tetracetate chelating agent 30g/L～50g/L, hydramine 10g/L～20g/L, Gemini type quaternary ammonium salt 3g/L～5g/L, sodium potassium tartrate tetrahydrate 5g/L～8g/L, dodecylbenzene sodium sulfonate 0.5g/L～1.5g/L, sodium hypophosphite 4g/L～10g/L, adding deionized water in the feed, the chemical bronze plating liquid being made into 1L is a。
It is preferred that, the raw material of described chemical bronze plating liquid includes mantoquita 15g/L, stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 2g/L, sodium ethylene diamine tetracetate chelating agent 40g/L, hydramine 15g/L, Gemini type quaternary ammonium salt 4g/L, sodium potassium tartrate tetrahydrate 6g/L, dodecylbenzene sodium sulfonate 1g/L, sodium hypophosphite 8g/L, adding deionized water in the feed, the chemical bronze plating liquid being made into 1L is a。
The pH value of described chemical bronze plating liquid is 11～12。
Described mantoquita can be one or more mixing in copper nitrate, copper sulfate, copper chloride, it is preferred to copper sulfate。
Chelating agent is for carrying out complexation with copper ion, through substantial amounts of experimentation, it has been found that the complexation effect adopting ethylenediaminetetraacetic acid is best, it is possible to well improve copper facing stability。
Described hydramine is carbon number be 2～6 a hydramine or glycol amine, it is possible to be in ethanolamine, Propanolamine, diethanolamine, dipropanolamine the mixture of one or two or more kinds composition。
Described 5-methyl-4-(preparation method of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole includes:
The first step, takes 2.93g (0.01mol) 6-methoxyl group-2-(2-bromine propiono) naphthalene, 30mL ethanol, 0.76g (0.01mol) thiourea, and reflux 3h, and ammonia adjusts pH value to be 8～9, and stirring is filtered, and dries to obtain light yellow solid；
Second step, the salicylide of 1mmol is dissolved in 5mL dehydrated alcohol, the ethanol solution that be slowly added dropwise prepared by 1mmol first step light yellow solid is stirred at room temperature down, finish, backflow 4h, cooling, sucking filtration, dehydrated alcohol recrystallization, obtains 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole。
The addition of this stabilizer can reduce the Auto-decomposition of chemical bronze plating liquid, be effectively improved the stability of chemical bronze plating liquid, can also regulate plating rate simultaneously, make copper deposit shinny, hence it is evident that improve the quality of coating。
The preparation method of described Gemini type quaternary ammonium salt includes:
The first step, 250ml there-necked flask adds 13.4g Disodium oxalate., 25.0g epoxychloropropane and 100ml dehydrated alcohol, reacts 10h in 50 DEG C under agitation, after having reacted, reaction system is down to room temperature, filters, remove the sodium chloride that reaction generates, by filtrate as 24h in-20 DEG C of refrigerator-freezers, crystallization, filters, and filter cake obtains intermediate as 24h dry in 50 DEG C of vacuum drying ovens after using-20 DEG C of ethanol rinse 3 times；
Second step, adds intermediate prepared by the 10.1g first step, 24.9g dodecyl-dimethyl amine hydrochlorate and 100ml dehydrated alcohol in 250ml there-necked flask, reacts 10h in 50 DEG C under agitation。After having reacted, reaction system is down to room temperature, filters, remove the sodium chloride that reaction generates, by filtrate as 24h, crystallization in-20 DEG C of refrigerator-freezers, filter, filter cake use less than after 5 DEG C of distilled water drip washing 3 times as 24h dry in 50 DEG C of vacuum drying ovens, Gemini quaternary surfactant of weighing to obtain。
The synthesis flow of described Gemini type quaternary ammonium salt is as follows:
Adopt Gemini quaternary surfactant provided by the invention, it is possible to reduce coating voidage, it is easier to plate layers of copper and coating uniform and delicate。
The preparation method that present invention also offers above-mentioned chemical copper plating solution, is specially and is mixed according to weight by above-mentioned each material composition, be configured to the solution of 1L。
Present invention also offers the using method of above-mentioned chemical copper plating solution, particularly as follows:
Above-mentioned chemical copper plating solution is warming up to 40 DEG C, with nitrogen to bubbling in this chemical bronze plating liquid, treated Kapton is soaked 4 hours in above-mentioned chemical bronze plating liquid；Kapton is taken out, with deionized water rinsing 1 minute, then adopts nitrogen air blast 4 minutes, obtain polyimides plating piece。
Hereinafter adopting embodiment to describe embodiments of the present invention in detail, to the present invention, how application technology means solve technical problem whereby, and the process that realizes reaching technique effect can fully understand and implement according to this。
The preparation of embodiment 1Gemini quaternary surfactant
250ml there-necked flask adds 13.4g Disodium oxalate., 25.0g epoxychloropropane and 100ml dehydrated alcohol, 10h is reacted under agitation in 50 DEG C, after having reacted, reaction system is down to room temperature, filter, remove the sodium chloride that reaction generates, by filtrate as 24h in-20 DEG C of refrigerator-freezers, crystallization, filter, filter cake obtains intermediate as 24h dry in 50 DEG C of vacuum drying ovens after using-20 DEG C of ethanol rinse 3 times, 250ml there-necked flask adds intermediate prepared by the 10.1g first step, 24.9g dodecyl-dimethyl amine hydrochlorate and 100ml dehydrated alcohol, 10h is reacted under agitation in 50 DEG C。After having reacted, reaction system is down to room temperature, filters, remove the sodium chloride that reaction generates, by filtrate as 24h, crystallization in-20 DEG C of refrigerator-freezers, filter, filter cake use less than after 5 DEG C of distilled water drip washing 3 times as 24h dry in 50 DEG C of vacuum drying ovens, Gemini quaternary ammonium salt of weighing to obtain。
EQUINX55 type Fourier transform infrared spectrometer is used for testing the characteristic absorption group of the Gemini quaternary surfactant of preparation。KBr tabletting, scanning times is 5 times, carries out infrared absorption measurement, and the infrared spectrum of record 500～4000cm-1 scope, result is as shown in Figure 1。
The embodiment 25-methyl-4-(preparation of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole
Take 2.93g (0.01mol) 6-methoxyl group-2-(2-bromine propiono) naphthalene, 30mL ethanol, 0.76g (0.01mol) thiourea, backflow 3h, ammonia adjusts pH value to be 8～9, stirring, filter, dry to obtain light yellow solid, the salicylide of 1mmol is dissolved in 5mL dehydrated alcohol, the ethanol solution that be slowly added dropwise prepared by 1mmol first step light yellow solid is stirred at room temperature down, finish, backflow 4h, cooling, sucking filtration, dehydrated alcohol recrystallization, obtain 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole, the collection of illustrative plates of its 1HNMR is as shown in Figure 2。
The preparation of embodiment 3 chemical bronze plating liquid 1
Stabilizer 5-methyl-4-(the Gemini type quaternary ammonium salt 4g of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 2g, sodium ethylene diamine tetracetate chelating agent 40g, diethanolamine 15g, embodiment 1 preparation, sodium potassium tartrate tetrahydrate 6g, dodecylbenzene sodium sulfonate 1g prepared by 15g copper sulfate, embodiment 2, sodium hypophosphite 8g joins in 300ml deionized water, stir, further add deionized water to 1000ml, stir 30 minutes, it is thus achieved that chemical bronze plating liquid 1。
The preparation of embodiment 4 chemical bronze plating liquid 2
Stabilizer 5-methyl-4-(the Gemini type quaternary ammonium salt 3g of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 1g, sodium ethylene diamine tetracetate chelating agent 30g, diethanolamine 10g, embodiment 1 preparation, sodium potassium tartrate tetrahydrate 5g, dodecylbenzene sodium sulfonate 0.5g prepared by 10g copper sulfate, embodiment 2, sodium hypophosphite 4g joins in 300ml deionized water, stir, further add deionized water to 1000ml, stir 30 minutes, it is thus achieved that chemical bronze plating liquid 2。
The preparation of embodiment 5 chemical bronze plating liquid 3
Stabilizer 5-methyl-4-(the Gemini type quaternary ammonium salt 5g of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 3g, sodium ethylene diamine tetracetate chelating agent 50g, diethanolamine 20g, embodiment 1 preparation, sodium potassium tartrate tetrahydrate 8g, dodecylbenzene sodium sulfonate 1.5g prepared by 20g copper sulfate, embodiment 2, sodium hypophosphite 10g joins in 300ml deionized water, stir, further add deionized water to 1000ml, stir 30 minutes, it is thus achieved that chemical bronze plating liquid 3。
The preparation of comparative example 1 chemical bronze plating liquid 4
Gemini type quaternary ammonium salt 4g prepared by 15g copper sulfate, sodium ethylene diamine tetracetate chelating agent 40g, diethanolamine 15g, embodiment 1, sodium potassium tartrate tetrahydrate 6g, dodecylbenzene sodium sulfonate 1g, sodium hypophosphite 8g joins in 300ml deionized water, stir, further add deionized water to 1000ml, stir 30 minutes, it is thus achieved that chemical bronze plating liquid 4。
The preparation of comparative example 2 chemical bronze plating liquid 5
Stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 2g, sodium ethylene diamine tetracetate chelating agent 40g, diethanolamine 15g, sodium potassium tartrate tetrahydrate 6g, dodecylbenzene sodium sulfonate 1g prepared by 15g copper sulfate, embodiment 2, sodium hypophosphite 8g joins in 300ml deionized water, stir, further add deionized water to 1000ml, stir 30 minutes, it is thus achieved that chemical bronze plating liquid 5。
The chemical copper plating solution of embodiment 1 to comparative example 2 is warming up to 40 DEG C respectively, with nitrogen to bubbling in this chemical bronze plating liquid, treated Kapton is soaked 4 hours in above-mentioned chemical bronze plating liquid。Kapton is taken out, with deionized water rinsing 1 minute, then adopts nitrogen air blast 4 minutes, obtain polyimides plating piece。If from starting chemical plating, decomposes (record from start chemistry be plated to the time now and be the plating solution resolving time) to plating solution, also not up to 4 hours, just plating piece has just been taken out in time Thickness Measurement by Microwave and plates fast。
The above-mentioned plating solution resolving time, namely well known to those skilled in the art, if being observed visually generation copper powder bottom plating solution, just illustrate that plating solution starts to decompose。The plating solution resolving time is more long, illustrates that the stability of plating solution is better, it is possible to plating is to obtain thicker coating for a long time, or can the multiple unplated piece of plating。If the plating solution resolving time is shorter, the less stable of plating solution is described, is unsuitable for long-time plating, therefore, be not suitable for the plating of relatively thickness coating。
Result is in Table 1 and table 2。
Table 1
| Group | The plating solution resolving time (hour) |
| Embodiment 1 | 4.67 |
| Embodiment 2 | 4.12 |
| Embodiment 3 | 4.33 5 --> |
| Comparative example 1 | 2.63 |
| Comparative example 2 | 4.03 |
As it can be seen from table 1 adopt chemical bronze plating liquid provided by the invention can improve the stability of copper plating bath significantly。
Table 2
| Group | Coating surface under scanning electron microscope (2000 times) | The outward appearance of perusal coating |
| Embodiment 1 | Coating is smooth, flawless | Red coating, bubble-free, color and luster is homogeneous |
| Embodiment 2 | Coating is smooth, flawless | Red coating, bubble-free, color and luster is homogeneous |
| Embodiment 3 | Coating is more smooth, without obvious crackle | Red coating, bubble-free, color and luster is homogeneous |
| Comparative example 1 | Coating is more smooth, without obvious crackle | Red coating, bubble-free, color and luster is homogeneous |
| Comparative example 2 | Coating has hole, out-of-flatness | Kermesinus coating, rough surface |
From table 2 it can be seen that adopt the plating of chemical bronze plating liquid provided by the invention more uniform, better effects if。
The above, be only presently preferred embodiments of the present invention, is not the restriction that the present invention makees other form, and any those skilled in the art are changed or be modified as the Equivalent embodiments of equivalent variations possibly also with the technology contents of the disclosure above。But every without departing from technical solution of the present invention content, according to any simple modification, equivalent variations and remodeling that above example is made by the technical spirit of the present invention, still fall within the protection domain of technical solution of the present invention。
Claims (6)
1. for the chemical bronze plating liquid of Kapton copper coating, it is characterized in that: raw material includes mantoquita 10g/L～20g/L, stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 1g/L～3g/L, sodium ethylene diamine tetracetate chelating agent 30g/L～50g/L, hydramine 10g/L～20g/L, Gemini type quaternary ammonium salt 3g/L～5g/L, sodium potassium tartrate tetrahydrate 5g/L～8g/L, dodecylbenzene sodium sulfonate 0.5g/L～1.5g/L, sodium hypophosphite 4g/L～10g/L, adding deionized water in the feed, the chemical bronze plating liquid being made into 1L is a；
Described mantoquita is one or more mixing in copper nitrate, copper sulfate, copper chloride；
Described hydramine is carbon number be 2～6 a hydramine or glycol amine。
2. the chemical bronze plating liquid for Kapton copper coating according to claim 1, it is characterized in that: described raw material includes mantoquita 15g/L, stabilizer 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole 2g/L, sodium ethylene diamine tetracetate chelating agent 40g/L, hydramine 15g/L, Gemini type quaternary ammonium salt 4g/L, sodium potassium tartrate tetrahydrate 6g/L, dodecylbenzene sodium sulfonate 1g/L, sodium hypophosphite 8g/L, adding deionized water in the feed, the chemical bronze plating liquid being made into 1L is a。
3. as claimed in claim 1 or 2 for the chemical bronze plating liquid of Kapton copper coating, it is characterised in that: the pH value of described chemical bronze plating liquid is 11～12。
4. as claimed in claim 3 for the chemical bronze plating liquid of Kapton copper coating, it is characterised in that: described 5-methyl-4-(preparation method of 6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole includes,
The first step, takes 2.93g (0.01mol) 6-methoxyl group-2-(2-bromine propiono) naphthalene, 30mL ethanol, 0.76g (0.01mol) thiourea, and reflux 3h, and ammonia adjusts pH value to be 8～9, and stirring is filtered, and dries to obtain light yellow solid；
Second step, the salicylide of 1mmol is dissolved in 5mL dehydrated alcohol, the ethanol solution that be slowly added dropwise prepared by 1mmol first step light yellow solid is stirred at room temperature down, finish, backflow 4h, cooling, sucking filtration, dehydrated alcohol recrystallization, obtains 5-methyl-4-(6-methoxyl group-2-naphthyl-2-(2-hydroxyl benzyl imino group) thiazole。
5. as claimed in claim 3 for Kapton copper coating chemical bronze plating liquid, it is characterised in that: the preparation method of described Gemini type quaternary ammonium salt includes,
The first step, adds 13.4g Disodium oxalate., 25.0g epoxychloropropane and 100ml dehydrated alcohol in 250ml there-necked flask, reacts 10h in 50 DEG C under agitation, after having reacted, reaction system is down to room temperature, filter, remove the sodium chloride that reaction generates；By filtrate as 24h in-20 DEG C of refrigerator-freezers, crystallization, filter, filter cake obtains intermediate as 24h dry in 50 DEG C of vacuum drying ovens after using-20 DEG C of ethanol rinse 3 times；
Second step, adds intermediate prepared by the 10.1g first step, 24.9g dodecyl-dimethyl amine hydrochlorate and 100ml dehydrated alcohol in 250ml there-necked flask, reacts 10h in 50 DEG C under agitation。After having reacted, reaction system is down to room temperature, filters, remove the sodium chloride that reaction generates, by filtrate as 24h, crystallization in-20 DEG C of refrigerator-freezers, filter, filter cake use less than after 5 DEG C of distilled water drip washing 3 times as 24h dry in 50 DEG C of vacuum drying ovens, obtain Gemini quaternary ammonium salt。
6. as claimed in claim 1 for the using method of the chemical bronze plating liquid of Kapton copper coating, it is characterised in that:
Described chemical copper plating solution is warming up to 40 DEG C, with nitrogen to bubbling in this chemical bronze plating liquid, treated Kapton is soaked 4 hours in above-mentioned chemical bronze plating liquid；Kapton is taken out, with deionized water rinsing 1 minute, then adopts nitrogen air blast 4 minutes, obtain polyimides plating piece。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410137110.2A CN103966582B (en) | 2014-04-04 | 2014-04-04 | The chemical bronze plating liquid of copper coating and using method for Kapton |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410137110.2A CN103966582B (en) | 2014-04-04 | 2014-04-04 | The chemical bronze plating liquid of copper coating and using method for Kapton |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103966582A CN103966582A (en) | 2014-08-06 |
| CN103966582B true CN103966582B (en) | 2016-06-22 |
Family
ID=51236572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410137110.2A Expired - Fee Related CN103966582B (en) | 2014-04-04 | 2014-04-04 | The chemical bronze plating liquid of copper coating and using method for Kapton |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103966582B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104313553B (en) * | 2014-09-26 | 2016-07-06 | 丽水学院 | Chemical bronze plating liquid of copper coating for Kapton and preparation method thereof, using method |
| WO2021023164A1 (en) | 2019-08-02 | 2021-02-11 | 云丁网络技术(北京)有限公司 | Intelligent lock control method and system |
| CN111408415A (en) * | 2020-04-16 | 2020-07-14 | 桂林电子科技大学 | Preparation method of Cotton/PPy/MWCNTs composite photocatalytic fabric for soil remediation |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5322976A (en) * | 1987-02-24 | 1994-06-21 | Polyonics Corporation | Process for forming polyimide-metal laminates |
| JP2002208768A (en) * | 2001-01-12 | 2002-07-26 | Hitachi Ltd | Method for forming metal plated film onto polyimide substrate |
| CN1858301A (en) * | 2006-06-08 | 2006-11-08 | 上海交通大学 | Method for chemical plating polyimide film surface |
| CN101654775B (en) * | 2008-08-21 | 2011-03-30 | 比亚迪股份有限公司 | Chemical plating material and preparation method thereof |
| CN101684554B (en) * | 2008-09-23 | 2012-03-07 | 比亚迪股份有限公司 | Chemical copper plating solution for polyimide film and surface chemical copper plating method thereof |
| CN103540915B (en) * | 2013-11-12 | 2015-09-23 | 哈尔滨理工大学 | A kind of method of polyimide surface electroless copper |
-
2014
- 2014-04-04 CN CN201410137110.2A patent/CN103966582B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103966582A (en) | 2014-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102060983B1 (en) | Electroless copper plating compositions | |
| CN104040026B (en) | Chemical plating copper plating solution without formaldehyde | |
| CN102586764A (en) | Method for selectively metallizing a substrate and circuit board produced by this method | |
| KR102035497B1 (en) | Stabilized silver catalysts and methods | |
| KR20080005132A (en) | Environmentally friendly electroless copper compositions | |
| CN1924091A (en) | Aqueous solution for surface treatment of tin films and method for preventing discoloration of a tin film surface | |
| CN103966582B (en) | The chemical bronze plating liquid of copper coating and using method for Kapton | |
| KR20120066607A (en) | Plating catalyst and method | |
| JP6307266B2 (en) | Formaldehyde-free electroless copper plating composition and method | |
| CN1473207A (en) | Method for electroless nickel plating | |
| KR20120066608A (en) | Plating catalyst and method | |
| KR20080005126A (en) | Electroless copper and redox couples | |
| CN104313553B (en) | Chemical bronze plating liquid of copper coating for Kapton and preparation method thereof, using method | |
| CN110512199A (en) | A kind of chemical bronze plating liquid and preparation method thereof | |
| TWI553152B (en) | Catalysts for electroless metallization containing five-membered heterocyclic nitrogen compounds | |
| JP5676970B2 (en) | Production of polymer-containing substrates for metallization. | |
| JP2012052222A (en) | Composition of nanoparticles | |
| Qin et al. | Metallization of polyester fabric by autocatalytic copper plating process using glyoxylic acid as a reducing agent | |
| JP6272673B2 (en) | Catalyst solution for electroless plating | |
| TWI582266B (en) | Alkaline plating bath for electroless deposition of cobalt alloys | |
| CN104213170A (en) | Copper plating method for high-order high-density circuit board | |
| CN105330821A (en) | Copolymers of diglycidyl ether terminated polysiloxane compounds and non-aromatic polyamines | |
| CN104250730B (en) | A kind of ionic palladium reducing solution and preparation method thereof and a kind of method of Chemical Plating of Non metal Material | |
| CN102560451B (en) | Chemical nano-silver plating solution and preparation method thereof, and silver plating method for copper part | |
| US9451707B2 (en) | Stabilized silver catalysts and methods |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Wang Xu Inventor before: Shen Qiuxian Inventor before: Wang Xu |
|
| COR | Change of bibliographic data | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Fu Yonghai Inventor before: Wang Xu |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20171222 Address after: 236800 Anhui Bozhou City Qiaocheng Xintiandi WAL-MART International Shopping Plaza, Bozhou Qiaocheng District, Guangming Road, Anhui Patentee after: Bozhou Jingxing Network Technology Co. Ltd. Address before: 323000 Lishui University Road, Liandu District, Lishui City, Zhejiang Province, No. 1 Patentee before: Lishui University |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180402 Address after: Three road 523000 in Guangdong province Dongguan City Qiaotou Shuikou stone village run No. 1 building B Patentee after: Dongguan sitande Electronic Materials Co., Ltd. Address before: 236800 Anhui Bozhou City Qiaocheng Xintiandi WAL-MART International Shopping Plaza, Bozhou Qiaocheng District, Guangming Road, Anhui Patentee before: Bozhou Jingxing Network Technology Co. Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160622 Termination date: 20190404 |