CN114957768A - Surface modifier before chemical plating and polyphenylene sulfide base material surface functional modification method - Google Patents
Surface modifier before chemical plating and polyphenylene sulfide base material surface functional modification method Download PDFInfo
- Publication number
- CN114957768A CN114957768A CN202210812173.8A CN202210812173A CN114957768A CN 114957768 A CN114957768 A CN 114957768A CN 202210812173 A CN202210812173 A CN 202210812173A CN 114957768 A CN114957768 A CN 114957768A
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- China
- Prior art keywords
- polyphenylene sulfide
- base material
- concentration
- treatment
- sulfide base
- 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.)
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 109
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 98
- 239000000126 substance Substances 0.000 title claims abstract description 38
- 238000007747 plating Methods 0.000 title claims abstract description 35
- 239000003607 modifier Substances 0.000 title claims abstract description 13
- 238000002715 modification method Methods 0.000 title claims abstract description 11
- 238000011282 treatment Methods 0.000 claims abstract description 56
- 238000001465 metallisation Methods 0.000 claims abstract description 10
- -1 phenolic amine compounds Chemical class 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 73
- 239000000758 substrate Substances 0.000 claims description 42
- 230000004048 modification Effects 0.000 claims description 31
- 238000012986 modification Methods 0.000 claims description 31
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 206010042674 Swelling Diseases 0.000 claims description 26
- 230000008961 swelling Effects 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 21
- 230000004913 activation Effects 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 16
- 238000006557 surface reaction Methods 0.000 claims description 16
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- 238000004140 cleaning Methods 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 12
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 12
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 12
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 12
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- 230000003064 anti-oxidating effect Effects 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 238000007772 electroless plating Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- JWZZKOKVBUJMES-UHFFFAOYSA-N (+-)-Isoprenaline Chemical compound CC(C)NCC(O)C1=CC=C(O)C(O)=C1 JWZZKOKVBUJMES-UHFFFAOYSA-N 0.000 claims description 2
- OGSPWJRAVKPPFI-UHFFFAOYSA-N Alendronic Acid Chemical compound NCCCC(O)(P(O)(O)=O)P(O)(O)=O OGSPWJRAVKPPFI-UHFFFAOYSA-N 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims 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 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 229960004343 alendronic acid Drugs 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 229940039009 isoproterenol Drugs 0.000 claims description 2
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- QNIVIMYXGGFTAK-UHFFFAOYSA-N octodrine Chemical compound CC(C)CCCC(C)N QNIVIMYXGGFTAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 2
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 2
- 239000012279 sodium borohydride Substances 0.000 claims description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 abstract description 85
- 239000010410 layer Substances 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 18
- 239000002184 metal Substances 0.000 abstract description 18
- 238000006845 Michael addition reaction Methods 0.000 abstract description 4
- 239000002262 Schiff base Substances 0.000 abstract description 4
- 150000004753 Schiff bases Chemical class 0.000 abstract description 4
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000002346 layers by function Substances 0.000 abstract description 2
- 239000002923 metal particle Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 230000001939 inductive effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 229910052802 copper Inorganic materials 0.000 description 14
- 239000010949 copper Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000007983 Tris buffer Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920001661 Chitosan Polymers 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002932 luster Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- AJAMDKATKXGWKD-UHFFFAOYSA-M sodium manganese(2+) oxygen(2-) hydroxide Chemical compound [OH-].[Na+].[O-2].[Mn+2] AJAMDKATKXGWKD-UHFFFAOYSA-M 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2053—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment only one step pretreatment
- C23C18/2066—Use of organic or inorganic compounds other than metals, e.g. activation, sensitisation with polymers
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
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- C23C18/40—Coating with copper using reducing agents
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract
The invention relates to the technical field of surface pretreatment and surface metallization of polyphenylene sulfide base materials, and discloses a surface modifier before chemical plating and a surface functional modification method of a polyphenylene sulfide base material. Aiming at solving the problem that a high-quality metal layer is difficult to deposit under the condition of ensuring the smaller roughness of the surface of the polyphenylene sulfide base material, the main scheme is as follows: firstly, pretreating the polyphenylene sulfide base material through microetching to improve the surface performance of the polyphenylene sulfide base material, then carrying out self-assembly on the surface of the microetched base material through Michael addition and Schiff base oxidation polymerization reaction which are carried out by phenolic amine compounds, and inducing active oxygen to generate accelerated deposition efficiency of the monomolecular functional layer through proper ultraviolet irradiation treatment, so that active groups capable of generating strong bonding action with metal particles can be introduced into the surface of the base material, and further high interface bonding strength between the polyphenylene sulfide base material and a chemically deposited metal layer is realized.
Description
Technical Field
The invention mainly relates to the technical field of surface pretreatment and polyphenylene sulfide surface metallization, in particular to a surface modifier before chemical plating and a polyphenylene sulfide base material surface functional modification method.
Background
The polyphenylene sulfide base material has good mechanical property, dimensional stability, corrosion resistance, low dielectric property, low dielectric loss, wide use frequency range, temperature resistance, flame retardance and other good physicochemical properties, and the surface of the polyphenylene sulfide base material can have electric conduction, heat conduction and other related metal characteristics by plating a metal layer on the surface of the polyphenylene sulfide base material, so that the polyphenylene sulfide base material can be widely applied to the fields of electronic communication, new energy automobiles, precise instruments, petrochemical industry, aviation national defense and the like.
Because the surface roughness of the polyphenylene sulfide base material is small, the free energy is low, the surface is hydrophobic and lacks active functional groups for adsorbing metal particles, the surface metallization is difficult to realize, and the bonding strength of the metal layer prepared on the surface and the polyphenylene sulfide base material is weak. In order to realize the surface metallization of the polyphenylene sulfide base material and improve the interface bonding strength between the surface metal layer and the base material, the surface modification of the polyphenylene sulfide is required before chemical plating, and the conventional modification method for the organic polymer base materials such as the polyphenylene sulfide mainly comprises swelling treatment, plasma treatment, sand blasting treatment, polymer auxiliary functional modification and the like. Chinese patent publication No. CN104017231A, a plastic surface treatment process, discloses a method for surface pretreatment of plastic by combining etching and swelling. Chinese patent CN110639362A, a method for preparing a catalytic fiber filter material by low-temperature plasma modification, discloses a method for preparing a fiber filter material by combining an electrostatic spinning technology and low-temperature plasma modification. Although the method can properly improve the surface performance of the organic polymer, the surface appearance of the base material can be damaged by excessive swelling treatment, so that the mechanical and electrical properties of the base material are influenced, the equipment required by plasma treatment is expensive, the energy consumption and the cost are high, and the uniformity of the surface of the base material is poor easily caused by sand blasting treatment, so that the polymer auxiliary functional modification becomes a simple and effective surface modification way.
The surface modifier is required to have a 'dual-property' structure when being selected, and the surface modifier has a molecular structure or a functional group which can form high-strength adhesion with the polyphenylene sulfide base material; secondly, the molecular structure or functional group can ensure the subsequent reaction to be completed smoothly; in the chinese patent CN101126156A, a process for chemical plating pretreatment of ABS plastic substrates, the chelating effect of chitosan and its derivatives on palladium catalyst is utilized to replace the physical bonding effect of traditional non-conductive substrate surface chemical plating pretreatment on palladium catalyst by chemical bonding effect. However, chitosan is only soluble in a part of acidic solutions, and the molecular structure of chitosan can be greatly changed under different pH values and temperature conditions, which limits the use of chitosan on organic polymer substrates such as polyphenylene sulfide substrates. Chinese patent CN110540662A, a preparation method of polydopamine modified carbon fiber/mullite whisker reinforced resin-based friction material, discloses that the interface bonding strength of carbon fiber/mullite whisker is obviously improved by a polydopamine surface modification method, and the friction and wear properties, heat resistance and mechanical properties of the composite material are improved. However, dopamine is expensive and has a long polymerization time, which limits its further industrial application.
Under the circumstance, in order to realize the surface metallization of the polyphenylene sulfide base material simply, efficiently and at low cost, it is important to find a surface modification method before chemical plating, which has the advantages of simple process flow, low equipment cost, strong applicability and high interface strength between a deposited metal layer and the polyphenylene sulfide base material.
Disclosure of Invention
The invention provides a surface modifier before chemical plating and a method for performing surface functional modification on a polyphenylene sulfide base material by using the surface modifier before chemical plating, aims to effectively solve the problems that the surface of the polyphenylene sulfide base material is difficult to realize metallization and the bonding force with a metal layer is poor, and has the advantages of simplicity, high efficiency, economy and environmental protection.
In order to solve the problems, the invention provides the following technical scheme:
a surface modifier before chemical plating, the main component of which comprises a matrix surface cross-linking agent A and a matrix surface cross-linking agent B, wherein:
the matrix surface cross-linking agent A is one or any combination of alendronate sodium, trihydroxymethyl aminomethane, catechol, p-hydroxyphenol and isoproterenol, the mass concentration of the substances is 5-55 mmol/L, and the pH value is adjusted to 9.5.
The matrix surface cross-linking agent B is one or a combination of any more of 1, 5-dimethylhexylamine, polyoxyethylene diamine, diethylenetriamine, tetraethylenepentamine and m-xylene diamine, and the mass concentration of the substances is 5-40 mmol/L.
The invention also discloses a method for functionally modifying the surface of the polyphenylene sulfide base material, which comprises the following steps;
soaking the cleaned polyphenylene sulfide base material into an alkaline swelling solution for swelling treatment;
step (2), performing micro-etching treatment on the surface of the polyphenylene sulfide base material treated in the step (1), and neutralizing residual micro-etching byproducts on the surface;
and (3) immersing the polyphenylene sulfide base material treated in the step (2) into a surface modifier before chemical plating, which is prepared from a matrix surface cross-linking agent A, a matrix surface cross-linking agent B and deionized water, and combining ultraviolet irradiation for functional modification, taking out, washing and drying, wherein after the phenolic amine reagent is combined with the ultraviolet irradiation, the spontaneous polymerization efficiency is higher and the cost is lower.
Step (4), activating and metalizing the polyphenylene sulfide base material subjected to surface functionalization modification, performing anti-oxidation treatment after the activation and metalizing, cleaning and drying to obtain a final sample;
in a further technical scheme, the alkaline swelling solution solvent in the step (1) is deionized water, the solute comprises one or more of N-methylpyrrolidone, ethyl acetoacetate, ethylene glycol diethyl ether, ethylene glycol butyl ether and sodium hydroxide, the concentration of the N-methylpyrrolidone is 20-80 mL/L, the concentration of the ethyl acetoacetate is 0-15 mL/L, the concentration of the ethylene glycol diethyl ether is 0-10 mL/L, the concentration of the ethylene glycol butyl ether is 5-40 mL/L, the concentration of the sodium hydroxide is 30-60 g/L, the swelling temperature is 30-70 ℃, and the swelling time is 5-30 min.
In a further technical scheme, the microetching solution used in the microetching treatment in the step (2) is a mixed solution of one or more of manganese dioxide, potassium permanganate, sodium pyrophosphate, concentrated sulfuric acid and potassium hydroxide, the concentration of manganese dioxide is 30-80 g/L, the concentration of potassium permanganate is 0-30 g/L, the concentration of sodium pyrophosphate is 30-60 g/L, the concentration of concentrated sulfuric acid is 350-800 mL/L, the concentration of potassium hydroxide is 30-60 g/L, the microetching temperature is 40-80 ℃, and the microetching time is 5-40 min.
In a further technical scheme, the solution for neutralizing the residual microetching byproducts on the surface in the step (2) is oxalic acid, the concentration is 10-50 g/L, the neutralization temperature is 30-70 ℃, and the neutralization time is 5-40 min.
In a further technical scheme, the polyphenylene sulfide in the step (3) is immersed in a surface modifier before chemical plating, wherein the concentration of the substrate surface cross-linking agent A is 5-55 mmol/L, the concentration of the substrate surface cross-linking agent B is 5-40 mmol/L, deionized water is used as a solvent, the treatment temperature is 20-50 ℃, the treatment time is 1-9 h, and the ultrasonic power is 50-200W.
In the further technical scheme, the activation treatment in the step (4) is carried out by using soluble silver salt, the concentration is 1-4 g/L, the activation temperature is 25-45 ℃, and the activation time is 5-25 min.
In a further technical scheme, the electroless plating solution used for the metallization treatment in the step (4) comprises copper sulfate, nickel sulfate, potassium ferrocyanide, potassium hydroxide, a stabilizer reducing agent and a complexing agent;
the stabilizer is one of bipyridyl and thiourea;
the reducing agent is one of sodium borohydride, formaldehyde and sodium hypochlorite;
the complexing agent is one or more of sodium citrate, potassium sodium tartrate, ethylenediamine and disodium ethylene diamine tetraacetate;
the treatment temperature is 35-60 ℃, and the treatment time is 20-80 min;
compared with the prior art, the invention has the following beneficial effects:
the matrix surface cross-linking agent A and the matrix surface cross-linking agent B can undergo Michael addition reaction with Schiff base through autoxidation to generate two oligomers, a high-adhesion-strength self-assembled monolayer can be formed on the surface of the polyphenylene sulfide base material through cross-linking coupling, and simultaneously a large number of hydroxyl and amino active groups can be introduced to improve the surface activity of the polyphenylene sulfide base material;
secondly, the metal copper layer prepared on the surface of the polyphenylene sulfide base material is flat, bright, uniform and compact, has extremely high purity and better crystallinity, and simultaneously has excellent mechanical property, electrical property and adhesive strength. The copper layer can still reach more than 90% of the initial conductivity after being exposed in the air for 72 days, and compared with the common chemical grafting modification treatment before chemical plating, the copper layer prepared on the surface of the polyphenylene sulfide base material has higher purity, better conductivity and better adhesion strength.
The method for functionally modifying the surface of the polyphenylene sulfide base material is simple and efficient in process flow and low in cost, a single-molecule functional layer can be formed on the surface of the base material through the Michael addition reaction between the matrix surface cross-linking agent A and the matrix surface cross-linking agent B and the Schiff base reaction, and two active groups, namely amino and hydroxyl, capable of generating a chelating effect with metal ions in chemical deposition liquid are introduced, so that a high-quality metal copper layer is finally prepared. The method effectively solves the problem that the surface of the polyphenylene sulfide base material is difficult to metalize, and has the advantages of simplicity, high efficiency, low cost and environmental protection.
According to the invention, the phenolic hydroxyl of the phenolic substance and the amino of the amine substance spontaneously generate Michael addition reaction and Schiff base reaction under the alkalescent condition to generate two different oligomers, the two oligomers form a crosslinking network rich in the phenolic hydroxyl and the amino through crosslinking coupling, and the crosslinking network can be firmly adsorbed on the surface of the base material, so that the polarity and the biological activity of the surface of the base material can be changed, and therefore, a large amount of active metal silver ions can be loaded on the surface of the base material, and a metal layer with good adhesion can be deposited on the surface of the base material.
Drawings
FIG. 1 is a schematic view of a process for performing surface functional modification and metallization on a polyphenylene sulfide substrate according to the present invention;
FIG. 2 is a surface X-ray photoelectron spectrum (XPS) of polyphenylene sulfide that is not activated by the surface functionalization modification and that is obtained by the surface functionalization modification activation of the present invention;
FIG. 3 is a comparison of optical microscopic morphology of surface copper layer obtained by electroless plating after surface functionalization modification and surface functionalization modification of polyphenylene sulfide.
Detailed Description
The invention is described in further detail below with reference to specific embodiments and the attached drawings.
The specific embodiment of the invention takes polyphenylene sulfide (PPS) as a base material, manganese dioxide-sodium pyrophosphate-concentrated sulfuric acid as a typical microetching solution, and the surface modification and metallization process flow is shown in figure 1.
Example 1
Surface swelling: sequentially adding sodium hydroxide, ethylene glycol monobutyl ether and N-methyl pyrrolidone into deionized water, fully stirring to obtain a swelling solution, heating the swelling solution to 50 ℃, then placing a polyphenylene sulfide (PPS) base material into the solution for treatment for 15min, taking out, washing and drying. The step has the main function of generating a micropore structure in the base material, because the base material has stronger acid and alkali corrosion resistance, the effect of directly carrying out micro-etching is not obvious, micropores can be formed in the base material through swelling treatment, the micro-etching liquid is favorably fully contacted with the base material, the micro-etching area is increased, and the effective micro-etching is favorably generated!
Surface micro-etching: adding manganese dioxide, sodium pyrophosphate and concentrated sulfuric acid (98%) into deionized water in sequence, fully stirring to obtain a coarsening solution, wherein the concentration of the manganese dioxide is 55g/L, the concentration of the sodium pyrophosphate is 60g/L, and the concentration of the concentrated sulfuric acid is 600mL/L, heating the coarsening solution to 50 ℃, and then putting the polyphenylene sulfide base material into the solution for treatment for 25 min. Then preparing a neutralization solution with the oxalic acid concentration of 35g/L and the sulfuric acid concentration of 120mL/L, cleaning and drying the microetched substrate, immersing the substrate in the neutralization solution, treating the substrate at the temperature of 60 ℃ for 15min, taking out the substrate, cleaning and drying the substrate.
Surface functional modification: adding a Tris (hydroxymethyl) aminomethane (Tris) buffer reagent into deionized water, adjusting the pH of the solution to about 9.5 by using dilute hydrochloric acid, then adding catechol and tetraethylenepentamine into the buffer solution, and fully stirring to obtain the matrix surface cross-linking agent, wherein the concentration of the Tris reagent is 15mmol/L, the concentration of the catechol is 20mmol/L, and the concentration of the tetraethylenepentamine is 10 mmol/L. And then soaking the clean polyphenylene sulfide after neutralization treatment in the solution at the ultrasonic intensity of 150W and the normal temperature for 3h, then placing the polyphenylene sulfide into an ultraviolet box with the wavelength of 365nm for irradiation treatment for 1h, and after the treatment is finished, washing and drying to obtain the polyphenylene sulfide base material with the surface functionalized and modified.
And (3) activation: adding silver nitrate with the concentration of 2.5g/L into deionized water, stirring to obtain an activation solution, and placing the polyphenylene sulfide with the surface functionalized modification into the activation solution to treat for 10min at 35 ℃. And after the treatment is finished, ultrasonically cleaning the polyphenylene sulfide substrate for many times by using deionized water, and drying the polyphenylene sulfide substrate to obtain the activated polyphenylene sulfide substrate.
Chemical plating: preparing chemical plating solution, heating the chemical plating solution to 50 ℃, placing the activated polyphenylene sulfide base material into the plating solution for treatment for 30min, taking out the base material, washing the base material with deionized water, placing the base material into benzotriazole solution of 6g/L for anti-oxidation treatment, and then annealing at high temperature to obtain the surface-metallized polyphenylene sulfide base material.
In the embodiment 1, the metal copper layer prepared on the surface of the polyphenylene sulfide base material has obvious metal luster, is uniform and compact, and the adhesive force between the base material and the copper layer is greatly improved and can reach 5B level in the ASTM-D3359 standard.
Example 2
Surface swelling: sequentially adding sodium hydroxide, ethylene glycol monobutyl ether and N-methyl pyrrolidone into deionized water, fully stirring to obtain a swelling solution, heating the swelling solution to 30 ℃, putting a polyphenylene sulfide (PPS) base material into the solution for treatment for 5min, taking out, washing and drying.
Surface micro-etching: adding manganese dioxide, sodium pyrophosphate, concentrated sulfuric acid (98%), potassium permanganate and potassium hydroxide into deionized water in sequence, fully stirring to obtain a coarsening solution, wherein the concentration of the manganese dioxide is 30g/L, the concentration of the sodium pyrophosphate is 30g/L, the concentration of the potassium permanganate is 0g/L, the concentration of the potassium hydroxide is 30g/L, the concentration of the concentrated sulfuric acid is 350mL/L, heating the coarsening solution to 40 ℃, and then placing the polyphenylene sulfide base material into the solution for treatment for 5 min. Then preparing a neutralization solution with the oxalic acid concentration of 10g/L and the sulfuric acid concentration of 120mL/L, cleaning and drying the microetched substrate, immersing the substrate in the neutralization solution, treating the substrate at the temperature of 30 ℃ for 5min, taking out the substrate, cleaning and drying the substrate.
Surface functional modification: adding a Tris (hydroxymethyl) aminomethane (Tris) buffer reagent into deionized water, adjusting the pH of the solution to about 9.5 by using dilute hydrochloric acid, then adding catechol and tetraethylenepentamine into the buffer solution, and fully stirring to obtain the matrix surface cross-linking agent, wherein the concentration of the Tris reagent is 15mmol/L, the concentration of the catechol is 5mmol/L, and the concentration of the tetraethylenepentamine is 5 mmol/L. And then soaking the clean polyphenylene sulfide after neutralization treatment in the solution at 50W ultrasonic intensity normal temperature for 1h, then placing the polyphenylene sulfide into an ultraviolet box with the wavelength of 365nm for irradiation treatment for 1h, and after the treatment is finished, washing and drying to obtain the polyphenylene sulfide base material with the surface functionalized and modified.
And (3) activation: adding silver nitrate with the concentration of 1g/L into deionized water, stirring to obtain an activation solution, and placing the polyphenylene sulfide with the surface functionalized and modified into the activation solution to treat for 5min at 25 ℃. And after the treatment is finished, ultrasonically cleaning the polyphenylene sulfide substrate for many times by using deionized water, and drying the polyphenylene sulfide substrate to obtain the activated polyphenylene sulfide substrate.
Chemical plating: preparing chemical plating solution, heating the chemical plating solution to 35 ℃, placing the activated polyphenylene sulfide base material into the plating solution for treatment for 20min, taking out the base material, washing the base material with deionized water, placing the base material into benzotriazole solution of 6g/L for anti-oxidation treatment, and then annealing at high temperature to obtain the surface-metallized polyphenylene sulfide base material.
In example 2, the metal copper layer prepared on the surface of the polyphenylene sulfide base material has obvious metal luster, is uniform and compact, and the adhesive force between the base material and the copper layer is greatly improved and can reach the 3B grade in the ASTM-D3359 standard.
Example 3
Surface swelling: sequentially adding sodium hydroxide, ethylene glycol monobutyl ether and N-methyl pyrrolidone into deionized water, fully stirring to obtain a swelling solution, heating the swelling solution to 70 ℃, then putting a polyphenylene sulfide (PPS) base material into the solution for treatment for 30min, taking out, washing and drying.
Surface micro-etching: adding manganese dioxide, sodium pyrophosphate, concentrated sulfuric acid (98%), potassium permanganate and potassium hydroxide into deionized water in sequence, fully stirring to obtain a coarsening solution, wherein the concentration of the manganese dioxide is 80g/L, the concentration of the sodium pyrophosphate is 60g/L, the concentration of the potassium permanganate is 30g/L, the concentration of the potassium hydroxide is 60g/L, the concentration of the concentrated sulfuric acid is 800mL/L, heating the coarsening solution to 80 ℃, and then putting the polyphenylene sulfide base material into the solution for treatment for 40 min. Then preparing a neutralization solution with oxalic acid concentration of 50g/L and sulfuric acid concentration of 120mL/L, cleaning and drying the microetched substrate, immersing the substrate in the neutralization solution, treating the substrate at 70 ℃ for 40min, taking out the substrate, cleaning and drying the substrate.
Surface functional modification: adding a Tris (hydroxymethyl) aminomethane (Tris) buffer reagent into deionized water, adjusting the pH of the solution to about 9.5 by using dilute hydrochloric acid, then adding catechol and tetraethylenepentamine into the buffer solution, and fully stirring to obtain the matrix surface cross-linking agent, wherein the concentration of the Tris reagent is 15mmol/L, the concentration of the catechol is 55mmol/L, and the concentration of the tetraethylenepentamine is 40 mmol/L. And then soaking the clean polyphenylene sulfide after neutralization treatment in the solution at the ultrasonic intensity of 200W and the normal temperature for 9h, then placing the polyphenylene sulfide into an ultraviolet box with the wavelength of 365nm for irradiation treatment for 1h, and after the treatment is finished, washing and drying to obtain the polyphenylene sulfide base material with the surface functionalized and modified.
And (3) activation: adding silver nitrate with the concentration of 4g/L into deionized water, stirring to obtain an activation solution, and placing the polyphenylene sulfide with the surface functionalized and modified into the activation solution to treat for 25min at 45 ℃. And after the treatment is finished, ultrasonically cleaning the polyphenylene sulfide substrate for many times by using deionized water, and drying the polyphenylene sulfide substrate to obtain the activated polyphenylene sulfide substrate.
Chemical plating: preparing chemical plating solution, heating the chemical plating solution to 60 ℃, placing the activated polyphenylene sulfide base material into the plating solution for treatment for 80min, taking out the base material, washing the base material with deionized water, placing the base material into benzotriazole solution of 6g/L for anti-oxidation treatment, and then annealing at high temperature to obtain the surface-metallized polyphenylene sulfide base material.
In example 3, the metal copper layer prepared on the surface of the polyphenylene sulfide base material has obvious metal luster, is uniform and compact, and the adhesion between the base material and the copper layer is greatly improved but does not reach the 4B grade in the ASTM-D3359 standard.
Comparative example
Surface swelling: sequentially adding sodium hydroxide, ethylene glycol monobutyl ether and N-methyl pyrrolidone into deionized water, fully stirring to obtain a swelling solution, heating the swelling solution to 50 ℃, then placing a polyphenylene sulfide (PPS) base material into the solution for treatment for 15min, taking out, washing and drying.
Surface micro-etching: adding manganese dioxide, sodium pyrophosphate and concentrated sulfuric acid (98%) into deionized water in sequence, fully stirring to obtain a coarsening solution, wherein the concentration of the manganese dioxide is 55g/L, the concentration of the sodium pyrophosphate is 60g/L, and the concentration of the concentrated sulfuric acid is 600mL/L, heating the coarsening solution to 50 ℃, and then putting the polyphenylene sulfide base material into the solution for treatment for 25 min. Then preparing a neutralization solution with the oxalic acid concentration of 35g/L and the sulfuric acid concentration of 120mL/L, cleaning and drying the microetched substrate, immersing the substrate in the neutralization solution, treating the substrate at the temperature of 60 ℃ for 15min, taking out the substrate, cleaning and drying the substrate.
And (3) activation: adding silver nitrate with the concentration of 2.5g/L into deionized water, stirring to obtain an activation solution, and placing the polyphenylene sulfide with the surface modification into the activation solution to treat for 10min at 35 ℃. And after the treatment is finished, ultrasonically cleaning the polyphenylene sulfide substrate for many times by using deionized water, and drying the polyphenylene sulfide substrate to obtain the activated polyphenylene sulfide substrate.
Chemical plating: preparing chemical plating solution, heating the chemical plating solution to 50 ℃, placing the activated polyphenylene sulfide base material into the plating solution for treatment for 30min, taking out the base material, washing the base material with deionized water, placing the base material into benzotriazole solution of 6g/L for anti-oxidation treatment, and then annealing at high temperature to obtain the surface-metallized polyphenylene sulfide base material.
FIG. 2 shows XPS after activation of polyphenylene sulfide which has not been subjected to surface functionalization modification in the comparative example and XPS after activation of polyphenylene sulfide which has been subjected to surface functionalization modification in the example. By comparison, it can be found that: the polyphenylene sulfide surface peak which is not subjected to functional modification is disordered, and the silver characteristic peak is not detected, while the polyphenylene sulfide surface which is subjected to functional modification can detect an obvious silver characteristic peak.
FIG. 3 shows the copper layer morphology after the polyphenylene sulfide electroless plating without surface functionalization modification in the comparative example and the copper layer morphology after the polyphenylene sulfide electroless plating with surface functionalization modification in the example. By comparison, the surface of the polyphenylene sulfide which is not subjected to surface functionalization modification is not plated with a complete copper layer after chemical plating, and the surface of the polyphenylene sulfide which is subjected to surface functionalization modification is bright, compact, uniform and flat after chemical plating.
Claims (8)
1. A surface modifier before chemical plating is characterized in that the main components comprise a matrix surface cross-linking agent A and a matrix surface cross-linking agent B, wherein:
the matrix surface cross-linking agent A is one or any combination of alendronate sodium, trihydroxymethyl aminomethane, catechol, p-hydroxyphenol and isoproterenol, the mass concentration of the substances is 5-55 mmol/L, and the pH value is adjusted to 9.5;
the matrix surface cross-linking agent B is one or a combination of any more of 1, 5-dimethylhexylamine, polyoxyethylene diamine, diethylenetriamine, tetraethylenepentamine and m-xylene diamine, and the mass concentration of the substances is 5-40 mmol/L.
2. A surface functionalization modification method of a polyphenylene sulfide base material is characterized by comprising the following steps:
soaking the cleaned polyphenylene sulfide base material into an alkaline swelling solution for swelling treatment;
step (2), performing micro-etching treatment on the surface of the polyphenylene sulfide base material treated in the step (1), and neutralizing residual micro-etching byproducts on the surface;
step (3), immersing the polyphenylene sulfide base material treated in the step (2) into a surface modifier before chemical plating, which is prepared by a matrix surface cross-linking agent A, a matrix surface cross-linking agent B and deionized water, and combining ultraviolet irradiation for functional modification, taking out, washing and drying;
and (4) activating and metalizing the polyphenylene sulfide base material subjected to surface functionalization modification, performing anti-oxidation treatment after the activation and metalizing, and cleaning and drying to obtain a final sample.
3. The surface functionalization modification method of the polyphenylene sulfide base material as claimed in claim 2, wherein the alkaline swelling solution solvent in the step (1) is deionized water, the solute is composed of one or more of N-methyl pyrrolidone, ethyl acetoacetate, ethylene glycol diethyl ether, ethylene glycol butyl ether and sodium hydroxide, the concentration of the N-methyl pyrrolidone is 20-80 mL/L, the concentration of the ethyl acetoacetate is 0-15 mL/L, the concentration of the ethylene glycol diethyl ether is 0-10 mL/L, the concentration of the ethylene glycol butyl ether is 5-40 mL/L, the concentration of the sodium hydroxide is 30-60 g/L, the swelling temperature is 30-70 ℃, and the swelling time is 5-30 min.
4. The surface functionalization modification method of the polyphenylene sulfide base material according to claim 2, wherein the microetching solution used in the surface microetching treatment in the step (2) is a mixed solution of one or more of manganese dioxide, potassium permanganate, sodium pyrophosphate, concentrated sulfuric acid and potassium hydroxide, the concentration of manganese dioxide is 30-80 g/L, the concentration of potassium permanganate is 0-30 g/L, the concentration of sodium pyrophosphate is 30-60 g/L, the concentration of concentrated sulfuric acid is 350-800 mL/L, the concentration of potassium hydroxide is 30-60 g/L, the microetching temperature is 40-80 ℃, and the microetching time is 5-40 min.
5. The method for functionally modifying the surface of a polyphenylene sulfide base material as claimed in claim 2, wherein the solution for neutralizing the residual microetching byproduct on the surface in step (2) is oxalic acid, the concentration is 10-50 g/L, the neutralization temperature is 30-70 ℃, and the neutralization time is 5-40 min.
6. The surface functionalization modification method of the polyphenylene sulfide base material, as claimed in claim 2, wherein the concentration of the substrate surface cross-linking agent A in the step (3) is 5-55 mmol/L, the concentration of the substrate surface cross-linking agent B is 5-40 mmol/L, deionized water is used as a solvent, the treatment temperature is 20-50 ℃, the treatment time is 1-9 h, and the ultrasonic power is 50-200W.
7. The method for functionally modifying the surface of a polyphenylene sulfide base material according to claim 2, wherein the activating treatment in step (4) is carried out using a soluble silver salt at a concentration of 1-4 g/L, an activating temperature of 25-45 ℃ and an activating time of 5-25 min.
8. The method for functionally modifying the surface of a polyphenylene sulfide substrate according to claim 2, wherein the electroless plating solution used in the metallization treatment in the step (4) comprises copper sulfate, nickel sulfate, potassium ferrocyanide, potassium hydroxide, a stabilizer reducing agent and a complexing agent;
the stabilizer is one of bipyridyl and thiourea;
the reducing agent is one of sodium borohydride, formaldehyde and sodium hypochlorite;
the complexing agent is one or more of sodium citrate, potassium sodium tartrate, ethylenediamine and disodium ethylene diamine tetraacetate;
the treatment temperature is 35-60 ℃, and the treatment time is 20-80 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116782516A (en) * | 2023-07-13 | 2023-09-19 | 南华大学 | Universal process for preparing copper printed circuit based on homogeneous ion type catalytic ink |
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| CN106436306A (en) * | 2016-06-14 | 2017-02-22 | 北京化工大学 | Surface modification method of fibers |
| CN111501030A (en) * | 2020-05-26 | 2020-08-07 | 电子科技大学 | Surface modification system before chemical plating and method for double modifying polymer substrate surface |
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| CN106436306A (en) * | 2016-06-14 | 2017-02-22 | 北京化工大学 | Surface modification method of fibers |
| CN111501030A (en) * | 2020-05-26 | 2020-08-07 | 电子科技大学 | Surface modification system before chemical plating and method for double modifying polymer substrate surface |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116782516A (en) * | 2023-07-13 | 2023-09-19 | 南华大学 | Universal process for preparing copper printed circuit based on homogeneous ion type catalytic ink |
| CN116782516B (en) * | 2023-07-13 | 2024-01-23 | 南华大学 | Universal process for preparing copper printed circuit based on homogeneous ion type catalytic ink |
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