CN113912976B - Application of molybdenum-containing sensitization auxiliary in laser activation selective metallization process of resin composition - Google Patents
Application of molybdenum-containing sensitization auxiliary in laser activation selective metallization process of resin composition Download PDFInfo
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- CN113912976B CN113912976B CN202111183957.0A CN202111183957A CN113912976B CN 113912976 B CN113912976 B CN 113912976B CN 202111183957 A CN202111183957 A CN 202111183957A CN 113912976 B CN113912976 B CN 113912976B
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- China
- Prior art keywords
- molybdenum
- laser
- resin composition
- sensitization auxiliary
- sensitization
- Prior art date
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- 206010070834 Sensitisation Diseases 0.000 title claims abstract description 114
- 230000008313 sensitization Effects 0.000 title claims abstract description 114
- 239000011342 resin composition Substances 0.000 title claims abstract description 79
- 230000004913 activation Effects 0.000 title claims abstract description 69
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 57
- 239000011733 molybdenum Substances 0.000 title claims abstract description 57
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims description 66
- 238000001465 metallisation Methods 0.000 title claims description 11
- 230000008569 process Effects 0.000 title claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 13
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 13
- GDXTWKJNMJAERW-UHFFFAOYSA-J molybdenum(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mo+4] GDXTWKJNMJAERW-UHFFFAOYSA-J 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims description 33
- -1 polypropylene Polymers 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 26
- 239000011347 resin Substances 0.000 claims description 26
- 239000012752 auxiliary agent Substances 0.000 claims description 22
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 14
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000007772 electroless plating Methods 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- QBJPPLLMLNMYAF-UHFFFAOYSA-N [Mo+4].[O-2].[Zn+2].[O-2].[O-2] Chemical compound [Mo+4].[O-2].[Zn+2].[O-2].[O-2] QBJPPLLMLNMYAF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 6
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 6
- HTIKCTPIJXASKS-UHFFFAOYSA-N aluminum molybdenum(4+) oxygen(2-) Chemical compound [O-2].[Al+3].[Mo+4] HTIKCTPIJXASKS-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- 239000000806 elastomer Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 2
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 claims description 2
- 229920002743 polystyrene-poly(ethylene-ethylene/propylene) block-polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical class [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 claims 2
- 238000007747 plating Methods 0.000 abstract description 16
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 230000003213 activating effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 229910052718 tin Inorganic materials 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002751 molybdenum Chemical class 0.000 abstract description 3
- 230000001235 sensitizing effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 49
- 229920003023 plastic Polymers 0.000 description 47
- 239000004033 plastic Substances 0.000 description 47
- 239000000843 powder Substances 0.000 description 34
- 230000000694 effects Effects 0.000 description 29
- 238000011056 performance test Methods 0.000 description 22
- 239000002985 plastic film Substances 0.000 description 22
- 238000010998 test method Methods 0.000 description 22
- 238000001746 injection moulding Methods 0.000 description 21
- 239000011159 matrix material Substances 0.000 description 21
- 238000001125 extrusion Methods 0.000 description 20
- 229920005601 base polymer Polymers 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000126 substance Substances 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 5
- PVGRIQYJDHKRFC-UHFFFAOYSA-N copper;oxomolybdenum Chemical compound [Cu].[Mo]=O PVGRIQYJDHKRFC-UHFFFAOYSA-N 0.000 description 5
- 238000010330 laser marking Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 4
- 229920005668 polycarbonate resin Polymers 0.000 description 4
- 239000004431 polycarbonate resin Substances 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000004901 spalling Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- XLTZWAZJMHGGRL-UHFFFAOYSA-N [O-2].[Ti+4].[Mo+4].[O-2].[O-2].[O-2] Chemical compound [O-2].[Ti+4].[Mo+4].[O-2].[O-2].[O-2] XLTZWAZJMHGGRL-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- BIOOACNPATUQFW-UHFFFAOYSA-N calcium;dioxido(dioxo)molybdenum Chemical compound [Ca+2].[O-][Mo]([O-])(=O)=O BIOOACNPATUQFW-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 2
- AGNOBAWAZFBMMI-UHFFFAOYSA-N dicesium dioxido(dioxo)molybdenum Chemical compound [Cs+].[Cs+].[O-][Mo]([O-])(=O)=O AGNOBAWAZFBMMI-UHFFFAOYSA-N 0.000 description 2
- XJUNRGGMKUAPAP-UHFFFAOYSA-N dioxido(dioxo)molybdenum;lead(2+) Chemical compound [Pb+2].[O-][Mo]([O-])(=O)=O XJUNRGGMKUAPAP-UHFFFAOYSA-N 0.000 description 2
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 description 2
- 238000005459 micromachining Methods 0.000 description 2
- WFLYOQCSIHENTM-UHFFFAOYSA-N molybdenum(4+) tetranitrate Chemical compound [N+](=O)([O-])[O-].[Mo+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] WFLYOQCSIHENTM-UHFFFAOYSA-N 0.000 description 2
- CZDSWLXAULJYPZ-UHFFFAOYSA-J molybdenum(4+);dicarbonate Chemical compound [Mo+4].[O-]C([O-])=O.[O-]C([O-])=O CZDSWLXAULJYPZ-UHFFFAOYSA-J 0.000 description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000007686 potassium Nutrition 0.000 description 2
- 239000011684 sodium molybdate Substances 0.000 description 2
- 235000015393 sodium molybdate Nutrition 0.000 description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 2
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229940049676 bismuth hydroxide Drugs 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 description 1
- NNLOHLDVJGPUFR-UHFFFAOYSA-L calcium;3,4,5,6-tetrahydroxy-2-oxohexanoate Chemical compound [Ca+2].OCC(O)C(O)C(O)C(=O)C([O-])=O.OCC(O)C(O)C(O)C(=O)C([O-])=O NNLOHLDVJGPUFR-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 102220157709 rs144942998 Human genes 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C23C18/1601—Process or apparatus
- C23C18/1603—Process or apparatus coating on selected surface areas
- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
-
- 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
-
- 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
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- 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
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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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
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Abstract
The invention provides an application of a molybdenum-containing sensitization auxiliary in preparing a resin composition capable of being selectively metallized by laser activation, wherein the molybdenum-containing sensitization auxiliary is selected from any one or more than two of molybdenum oxide, molybdenum sulfide, molybdenum hydroxide, molybdenum acid and molybdenum salt. The inventors of the present invention have unexpectedly found that electroless copper plating can be performed well on the surface of a resin composition containing a molybdenum-containing sensitizing assistant added thereto by activation with a laser having a wavelength of 190 to 1064 nm. On the one hand, 190-1064nm covers almost all laser wavelengths, and activating the resin composition at different laser wavelengths can exert the advantages of the laser wavelengths themselves; on the other hand, compared with the traditional sensitization auxiliary containing copper, tin and bismuth, the molybdenum-containing sensitization auxiliary has lower price, and can obviously reduce the production cost. The invention can obtain the resin composition with excellent coating thickness and coating strength under the condition of lower molybdenum-containing sensitization auxiliary addition amount, and has excellent industrial application value.
Description
Technical Field
The invention belongs to the field of laser sensitization auxiliary agents, and particularly relates to an application of a molybdenum-containing sensitization auxiliary agent in preparing a resin composition capable of being selectively metallized by laser activation.
Background
Laser activation selective metallization (LISM) is to control the movement of laser according to the track of the conductive pattern by using a computer, to irradiate the laser onto a molded three-dimensional plastic device, to activate the circuit pattern within a few seconds, and then to chemically plate the activated surface, so that metals such as copper, nickel, gold, etc. are deposited in the activated region to form a conductive circuit. With this process, not only high flexibility of production can be achieved, but also ultra-fine circuit fabrication and fine assembly can be made possible.
The laser activation selective metallization technology has the advantages of high production efficiency, low cost, small product volume, flexible design and high conductivity of the metal layer obtained by chemical plating. If the circuit pattern is to be changed, only the circuit pattern is required to be redesigned by a computer, and no extra mask is needed. Compared with the traditional selective metallization method, the laser-induced activation selective metallization has the characteristics of flexible design, short production period and suitability for large-scale production, and is widely applied to the fields of communication, electronic equipment, medical equipment and the like. Particularly, with the popularization of 5G communication, the conventional FRPC antenna and PDS antenna cannot meet the performance requirements of 5G mobile phones, and almost all smart mobile phones use LISM antennas.
Laser activated selective metallization is typically performed by activating the surface of the article with a laser and then depositing a metal layer on the laser activated areas using electroless plating to obtain the desired metal circuitry and pattern. However, most polymers have a weak absorption of laser light, and require the addition of specific sensitizing aids that both absorb laser energy and induce electroless plating. Currently, the types of conventional sensitization aids are quite limited, mainly compounds containing copper and tin metals, such as: copper-containing salts, tin-containing oxides, which are expensive and economically disadvantageous. The Chinese patent ZL201610154118.9 discloses a bismuth-containing sensitization auxiliary agent, mainly comprising bismuth oxide, bismuth sulfide, bismuth hydroxide, bismuth oxychloride or bismuth salt, wherein the dosage of the bismuth-containing sensitization auxiliary agent is low, the prepared resin composition containing the bismuth sensitization auxiliary agent has lighter ground color, the problem that the ground color of plastic is affected is solved to a certain extent, but the price of the bismuth-containing compound is high, and the economic benefit is still to be further improved. In addition, the bismuth-containing sensitization auxiliary agent can only be activated by adopting 1064nm near infrared laser, and cannot exert the advantages of lasers with other wavelengths.
In order to overcome the defects of the existing sensitization auxiliary, a laser sensitization auxiliary which has low cost, small addition amount, various activatable laser wavelengths and excellent laser activation effect and a laser activatable resin product with excellent further electroless plating effect need to be developed.
Disclosure of Invention
The invention aims to provide an application of a molybdenum-containing sensitization auxiliary in preparing a laser activation selective metallization resin composition, and a resin composition capable of being selectively metallized by laser activation and a laser activatable resin product with excellent electroless plating effect.
The invention provides an application of a molybdenum-containing sensitization auxiliary in preparing a laser activated selective metallization resin composition, wherein the molybdenum-containing sensitization auxiliary is selected from any one or more than two of molybdenum oxide, molybdenum sulfide, molybdenum hydroxide, molybdenum acid and molybdenum salt; the laser activation is carried out by using 190-1064nm wavelength laser.
Further, the molybdenum oxide is selected from any one or more than two of molybdenum trioxide, molybdenum dioxide, iron-doped molybdenum oxide, molybdenum aluminum oxide, molybdenum copper oxide, molybdenum zinc oxide and molybdenum titanium oxide;
and/or, the sulfide of molybdenum is molybdenum disulfide;
and/or, the hydroxide of molybdenum is molybdenum hydroxide;
and/or the acid containing molybdenum is any one or more than two of molybdic acid, phosphomolybdic acid and silicomolybdic acid;
and/or the molybdenum-containing salt is selected from any one or more than two of molybdenum phosphate, molybdenum sulfate, molybdenum nitrate, molybdenum silicate, molybdenum carbonate, molybdenum aluminate, molybdenum bismuthate, ammonium paramolybdate, ammonium molybdate, sodium molybdate, potassium molybdate, cesium molybdate, calcium molybdate, bismuth molybdate, nickel molybdate, zinc molybdate, lithium molybdate, lead molybdate, sodium phosphomolybdate, sodium silicomolybdate and niobium molybdate.
The invention also provides a resin composition capable of being selectively metallized by laser activation, which comprises the following components in percentage by weight: 1.0 to 55 percent of molybdenum-containing sensitization auxiliary agent and 45 to 99 percent of polymer; wherein the molybdenum-containing sensitization auxiliary is selected from any one or more than two of molybdenum oxide, molybdenum sulfide, molybdenum acid and molybdenum salt.
Further, it is composed of the following components in percentage by weight: 2% -50% of molybdenum-containing sensitization auxiliary agent and 50% -98% of polymer; preferably, it is composed of the following components in percentage by weight: 10-50% of molybdenum-containing sensitization auxiliary agent and 50-90% of polymer.
Further, the molybdenum oxide is selected from any one or more than two of molybdenum trioxide, molybdenum dioxide, iron-doped molybdenum oxide, molybdenum aluminum oxide, molybdenum copper oxide, molybdenum zinc oxide and molybdenum titanium oxide;
and/or, the sulfide of molybdenum is molybdenum disulfide;
and/or, the hydroxide of molybdenum is molybdenum hydroxide;
and/or the acid containing molybdenum is any one or more than two of molybdic acid, phosphomolybdic acid and silicomolybdic acid;
and/or the molybdenum-containing salt is selected from any one or more than two of molybdenum phosphate, molybdenum sulfate, molybdenum nitrate, molybdenum silicate, molybdenum carbonate, molybdenum aluminate, molybdenum bismuthate, ammonium paramolybdate, ammonium molybdate, sodium molybdate, potassium molybdate, cesium molybdate, calcium molybdate, bismuth molybdate, nickel molybdate, zinc molybdate, lithium molybdate, lead molybdate, sodium phosphomolybdate, sodium silicomolybdate and niobium molybdate.
Further, the average particle size of the molybdenum-containing sensitization auxiliary is less than or equal to 150 mu m; preferably, the average particle diameter of the molybdenum-containing sensitization auxiliary is 0.010 mu m-50 mu m; more preferably, the average particle diameter of the molybdenum-containing sensitization auxiliary is 0.05 μm to 20 μm.
Further, the polymer is selected from any one or more than two of polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polystyrene, K resin, styrene-acrylonitrile copolymer, PEN, polyphenyl ether, polyphenylene sulfide, polyether ether ketone, polyurethane, nylon elastomer, SEBS, SEPS, SEEPS and polyester elastomer.
The invention also provides a preparation method of the resin composition capable of being selectively metallized by laser activation, which comprises the following steps:
a. taking a molybdenum-containing sensitization auxiliary agent and a polymer, and uniformly mixing to obtain a mixture;
b. and d, carrying out melt blending and granulation on the mixture obtained in the step a to obtain the resin composition capable of being selectively metallized by laser activation.
The invention also provides application of the resin composition capable of being selectively metallized by laser activation in preparation of micro-machining materials, wherein the micro-machining materials comprise micro-circuit materials.
The invention also provides a fine circuit material, which is formed by selectively activating the resin composition under the laser with the wavelength of 190-1064nm and then performing electroless plating to deposit conductive metal on an activation area; preferably, the conductive metal is copper, nickel or gold.
Experimental results show that the molybdenum-containing sensitization auxiliary has low price and small addition amount, and can remarkably reduce the production cost of the selectively metallized product capable of being activated by laser. The molybdenum-containing sensitization auxiliary agent of the invention shows excellent laser activation capability under the laser action of the wavelength range of 190-1064nm, the prepared resin capable of being selectively metallized by laser activation has light color, good chemical plating effect after activation, the plating thickness of the obtained resin composition reaches more than 1.8 mu m under the condition of the addition amount as low as 1wt%, and the strength of the plating reaches the highest level of 5B under the test of a hundred-blade (ASTM D3359), thus having very broad application prospect.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Detailed Description
The materials and equipment used in the embodiments of the present invention are all known products and are obtained by purchasing commercially available products.
(1) The equipment information used in the invention is as follows:
a twin screw extruder, screw diameter 35mm, screw aspect ratio 36:1, manufactured by Nanj jenty electric company, inc;
injection molding machine, model MA600, produced by maritime machinery limited;
the laser marking machine is of the model MUV-E-R, the maximum power of the laser is 5W, and the laser wavelength is 355nm;
the laser marking machine is of a model MV-U, the maximum power of the laser is 3W, and the laser wavelength is 190nm;
the laser marking machine is of the model DZ-Q, the maximum power of the laser is 8W, and the laser wavelength is 395nm;
the laser marking machine is of the type MF-E-A, the maximum power of the laser is 20W, and the laser wavelength is 1064nm;
the laser marking machine is of the model YK-F20G, the maximum power of the laser is 10W, and the laser wavelength is 532nm.
(2) The specific information of the matrix polymer used for preparing the standard template is as follows:
polycarbonate: PC121R (density: 1.2g/cm3; melt flow rate: 17.5g/10min,300 ℃,1.2Kg; heat distortion temperature: 125 ℃).
Acrylonitrile-butadiene-styrene (ABS) Taiwan Qimen, PA757 (density: 1.05g/cm3; melt flow rate: 1.8g/10min,200 ℃ C., 5 Kg).
Polystyrene: GPPS-500 (density: 1.04g/cm3; melt flow rate: 5g/10min,200 ℃,5Kg; heat distortion temperature: 89 ℃ C.) is petrochemical, philippine.
Polyethylene terephthalate: CB-602 (density: 1.40g/cm3; melting temperature: 245 ℃ C.).
Polybutylene terephthalate: pasteff, germany, PBTB4500 (density: 1.3g/cm3; melting temperature: 230 ℃).
SEBS Japanese colali, HYBRA7311F (density: 0.89g/cm3; melting temperature: 200 ℃).
Polyamide 66: langsheng, germany, A30S (density: 1.14g/cm3; melting temperature: 260 ℃).
Polypropylene: daqing petrochemical, T30S (density: 0.9g/cm3; melting temperature: 189 ℃).
Polyethylene (PE): the name is petrochemical, TR144, a high density polyethylene (density: 0.95g/cm3; melt temperature: 142 ℃ C.).
Example 1
Firstly, 99g of ABS resin and 1g of laser sensitization auxiliary molybdenum trioxide powder (average particle diameter is 2 mu m) are fully mixed in a high-speed stirrer for 2 minutes; and then, placing the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 220 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
Then, the prepared resin composition capable of being selectively metallized by laser activation is injected into a plastic plate by an injection molding machine, and the injection molding temperature is 220 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has laser wavelength of 355nm, laser speed of 2000mm/s, laser energy of 2.5W and laser frequency of 60kHz.
According to the known chemical plating method and process of the laser activated selective metallization resin composition, the plastic plate after laser activation is subjected to chemical copper plating, copper sulfate is adopted as copper salt of metal in the chemical copper plating, the resin composition is placed into chemical copper plating solution for reaction copper plating, and air is continuously introduced in the middle to stir so as to ensure the uniformity of a copper layer.
After electroless copper plating, the following effect and/or performance tests were performed:
(1) Chemical plating effect: visual inspection;
(2) Plating thickness of electroless copper plating: testing according to astm b568 (2009);
(3) And (3) hundred-cell knife test: square small grids of 1mm x 1mm in size were scribed in copper plated areas using a scriber according to ASTM D3359. Next, the Scotch 3M600-1PK test tape was applied to the scribe area and the tape was quickly peeled off. And judging the grade of the adhesive strength according to the falling area of the copper layer. In the ASTM D3359 rating, a higher number of steps indicates a higher adhesion between the polymer substrate and the copper plating. Wherein:
the spalling area of the 0B grid is more than 65%;
the spalling area of the 1B grid is 35% -65%;
the spalling area of the 2B grid is 15% -35%;
the peeling area of the 3B grid is 5% -15%;
the spalling area of the 4B mesh was 5%;
5B had no flaking of any mesh.
The test results are shown in Table 1.
Example 2
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 1, with the only difference that the matrix polymer and the laser sensitization aid were: 95g of ABS resin and 5g of laser sensitization auxiliary molybdenum trioxide powder.
The test method was the same as in example 1, and the test results are shown in Table 1.
Example 3
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 1, with the only difference that the matrix polymer and the laser sensitization aid were: 90g of ABS resin and 10g of laser sensitization auxiliary molybdenum trioxide powder.
The test method was the same as in example 1, and the test results are shown in Table 1.
Example 4
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 1, with the only difference that the matrix polymer and the laser sensitization aid were: 80g of ABS resin and 20g of laser sensitization auxiliary molybdenum trioxide powder.
The test method was the same as in example 1, and the test results are shown in Table 1.
Example 5
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 1, with the only difference that the matrix polymer and the laser sensitization aid were: 50g of ABS resin and 50g of laser sensitization auxiliary molybdenum trioxide powder.
The test method was the same as in example 1, and the test results are shown in Table 1.
Example 6
99g of ABS resin and 1g of molybdenum dioxide powder (average particle diameter of 3 mu m) serving as a laser sensitization auxiliary agent are fully mixed in a high-speed stirrer for 3 minutes; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 215 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 210 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse near infrared laser has laser wavelength of 1064nm, speed of 2000mm/s, laser energy of 10W and laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 7
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 6, with the only difference that the matrix polymer and the laser sensitization aid were: 95g of ABS resin and 5g of laser sensitization auxiliary molybdenum dioxide powder.
The test method was the same as in example 6, and the test results are shown in Table 1.
Example 8
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 6, with the only difference that the matrix polymer and the laser sensitization aid were: 90g of ABS resin and 10g of laser sensitization auxiliary molybdenum dioxide powder.
The test method was the same as in example 6, and the test results are shown in Table 1.
Example 9
98g of polybutylene terephthalate resin and 2g of molybdenum aluminum oxide powder (average particle diameter of 6 mu m) as a laser sensitization auxiliary agent are fully mixed for 3 minutes in a high-speed stirrer; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 265 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 260 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has the laser wavelength of 395nm, the speed of 2000mm/s, the laser energy of 3W and the laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 10
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 9, with the only difference that the matrix polymer and the laser sensitization aid were: 95g of polybutylene terephthalate resin and 5g of laser sensitization auxiliary molybdenum oxide aluminum powder.
The test method was the same as in example 9, and the test results are shown in Table 1.
Example 11
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 9, with the only difference that the matrix polymer and the laser sensitization aid were: 90g of polybutylene terephthalate resin and 10g of laser sensitization auxiliary molybdenum oxide aluminum powder.
The test method was the same as in example 9, and the test results are shown in Table 1.
Example 12
98g of SEBS resin and 2g of molybdenum copper oxide powder (with the average particle size of 3 mu m) serving as a laser sensitization auxiliary agent are fully mixed in a high-speed stirrer for 3 minutes; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 200 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 195 ℃.
The plastic plate is subjected to laser activation under the following conditions: the green laser has a laser wavelength of 532nm, a speed of 2000mm/s, a laser energy of 5W and a laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 13
A laser activatable selectively metallized resin composition and a laser activated plastic panel were prepared according to the method of example 12, except that the base polymer and the laser sensitization aid were: 95g of SEBS resin and 5g of laser sensitization auxiliary molybdenum copper oxide powder.
The test method was the same as in example 12, and the test results are shown in Table 1.
Example 14
A laser activatable selectively metallized resin composition and a laser activated plastic panel were prepared according to the method of example 12, except that the base polymer and the laser sensitization aid were: 90g of SEBS resin and 10g of laser sensitization auxiliary molybdenum copper oxide powder.
The test method was the same as in example 12, and the test results are shown in Table 1.
Example 15
98g of polystyrene resin and 2g of laser sensitization auxiliary molybdenum zinc oxide powder (average particle diameter is 2 mu m) are fully mixed for 3 minutes in a high-speed stirrer; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 215 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 210 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse laser has the laser wavelength of 190nm, the speed of 2000mm/s, the laser energy of 1W and the laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 16
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 15, except that the base polymer and laser sensitization aid were: 95g of polystyrene resin and 5g of laser sensitization auxiliary molybdenum zinc oxide powder.
The test method was the same as in example 15, and the test results are shown in Table 1.
Example 17
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 15, except that the base polymer and laser sensitization aid were: 90g of polystyrene resin and 10g of laser sensitization auxiliary molybdenum zinc oxide powder.
The test method was the same as in example 15, and the test results are shown in Table 1.
Example 18
98g of polyethylene resin and 2g of laser sensitization auxiliary iron-doped molybdenum oxide powder (average particle size of 0.5 mu m) are fully mixed in a high-speed stirrer for 3 minutes; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 160 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 160 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse near infrared laser has laser wavelength of 1064nm, speed of 2000mm/s, laser energy of 12W and laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 19
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 18, except that the base polymer and laser sensitization aid were: 95g of polyethylene resin and 5g of laser sensitization auxiliary iron doped molybdenum oxide powder.
The test method was the same as in example 18, and the test results are shown in Table 1.
Example 20
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 18, except that the base polymer and laser sensitization aid were: 90g of polyethylene resin and 10g of laser sensitization auxiliary iron doped molybdenum oxide powder.
The test method was the same as in example 18, and the test results are shown in Table 1.
Example 21
97g of polypropylene resin and 3g of laser sensitization auxiliary molybdenum disulfide powder (average particle diameter is 4 mu m) are fully mixed for 3 minutes in a high-speed stirrer; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 195 ℃, and obtaining the resin composition capable of being activated by laser and selectively metallized.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 190 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has laser wavelength of 355nm, laser speed of 2000mm/s, laser energy of 3W and laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 22
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 21, with the only difference that the matrix polymer and the laser sensitization aid were: 90g of polypropylene resin and 10g of laser sensitization auxiliary molybdenum disulfide powder.
The test method was the same as in example 21, and the test results are shown in Table 1.
Example 23
A laser activatable selectively metallizable resin composition and a laser activated plastic sheet were prepared according to the method of example 21, with the only difference that the matrix polymer and the laser sensitization aid were: 80g of polypropylene resin and 20g of laser sensitization auxiliary molybdenum disulfide powder.
The test method was the same as in example 21, and the test results are shown in Table 1.
Example 24
97g of polyethylene terephthalate resin and 3g of laser sensitization auxiliary molybdenum hydroxide powder (average particle size is 8 mu m) are fully mixed in a high-speed stirrer for 3 minutes; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 240 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 240 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse laser has the laser wavelength of 190nm, the speed of 2000mm/s, the laser energy of 1W and the laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 25
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 24, except that the base polymer and laser sensitization aid were: 90g of polyethylene terephthalate resin and 10g of laser sensitization auxiliary molybdenum hydroxide powder.
The test method was the same as in example 24, and the test results are shown in Table 1.
Example 26
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 24, except that the base polymer and laser sensitization aid were: 80g of polyethylene terephthalate resin and 20g of laser sensitization auxiliary molybdenum hydroxide powder.
The test method was the same as in example 24, and the test results are shown in Table 1.
Example 27
97g of polycarbonate resin and 3g of laser sensitization auxiliary molybdic acid powder (average particle diameter is 4 μm) were thoroughly mixed in a high-speed stirrer for 3 minutes; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 265 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 260 ℃.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has the laser wavelength of 395nm, the speed of 2000mm/s, the laser energy of 4W and the laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 28
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 27, except that the base polymer and laser sensitization aid were: 90g of polycarbonate resin and 10g of laser sensitization auxiliary molybdic acid powder.
The test method was the same as in example 27, and the test results are shown in Table 1.
Example 29
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 27, except that the base polymer and laser sensitization aid were: 80g of polycarbonate resin and 20g of laser sensitization auxiliary molybdic acid powder.
The test method was the same as in example 27, and the test results are shown in Table 1.
Example 30
95g of polyamide 66 resin and 5g of laser sensitization auxiliary molybdenum phosphate powder (average particle diameter is 2 mu m) are fully mixed for 3 minutes in a high-speed stirrer; and then, putting the mixed materials into a double-screw extruder for melt extrusion, granulating, wherein the extrusion temperature is 265 ℃, and obtaining the resin composition capable of being selectively metallized by laser activation.
And (3) injecting the prepared resin composition capable of being selectively metallized through laser activation into a plastic plate through an injection molding machine, wherein the injection molding temperature is 260 ℃.
The plastic plate is subjected to laser activation under the following conditions: the green laser has a laser wavelength of 532nm, a speed of 2000mm/s, a laser energy of 6W and a laser frequency of 80kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Example 31
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 30, except that the base polymer and laser sensitization aid were: 90g of polyamide 66 resin and 10g of laser sensitization auxiliary molybdenum phosphate powder.
The test method was the same as in example 30, and the test results are shown in Table 1.
Example 32
The laser activatable selectively metallized resin composition and laser activated plastic sheeting were prepared in accordance with the method of example 30, except that the base polymer and laser sensitization aid were: 80g of polyamide 66 resin and 20g of laser sensitization auxiliary molybdenum phosphate powder.
The test method was the same as in example 30, and the test results are shown in Table 1.
Comparative example 1
Resin compositions and plastic sheets that can be selectively metallized by laser activation were prepared according to the method of example 1, except that the base polymer and the laser sensitization aid were: 99.5g of ABS resin and 0.5g of laser sensitization auxiliary molybdenum trioxide powder.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has laser wavelength of 355nm, laser speed of 2000mm/s, laser energy of 2.5W and laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 2
Resin compositions and plastic sheets that can be selectively metallized by laser activation were prepared according to the method of example 1, except that the base polymer and the laser sensitization aid were: 99.5g of ABS resin and 0.5g of laser sensitization auxiliary molybdenum dioxide powder.
The plastic plate is subjected to laser activation under the following conditions: the pulse near infrared laser has laser wavelength of 1064nm, speed of 2000mm/s, laser energy of 10W and laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 3
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of ABS resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has laser wavelength of 355nm, laser speed of 2000mm/s, laser energy of 2.5W and laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 4
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of ABS resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse near infrared laser has laser wavelength of 1064nm, speed of 2000mm/s, laser energy of 10W and laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 5
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of polybutylene terephthalate resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has the laser wavelength of 395nm, the speed of 2000mm/s, the laser energy of 3W and the laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 6
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of SEBS resin.
The plastic plate is subjected to laser activation under the following conditions: the green laser has a laser wavelength of 532nm, a speed of 2000mm/s, a laser energy of 5W and a laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 7
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of polystyrene resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse laser has the laser wavelength of 190nm, the speed of 2000mm/s, the laser energy of 1W and the laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 8
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of polyethylene resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse near infrared laser has laser wavelength of 1064nm, speed of 2000mm/s, laser energy of 12W and laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 9
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of polypropylene resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has laser wavelength of 355nm, laser speed of 2000mm/s, laser energy of 3W and laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 10
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of polyethylene terephthalate resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse laser has the laser wavelength of 190nm, the speed of 2000mm/s, the laser energy of 1W and the laser frequency of 50kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 11
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of polycarbonate resin.
The plastic plate is subjected to laser activation under the following conditions: the pulse ultraviolet laser has the laser wavelength of 395nm, the speed of 2000mm/s, the laser energy of 4W and the laser frequency of 60kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Comparative example 12
The plastic sheet was prepared by the method of reference example 1, except that no laser sensitization aid was added, and the matrix polymer was: 100g of polyamide 66 resin.
The plastic plate is subjected to laser activation under the following conditions: the green laser has a laser wavelength of 532nm, a speed of 2000mm/s, a laser energy of 6W and a laser frequency of 80kHz.
The effect and/or performance test methods were the same as in example 1, and the test results are shown in Table 1.
Table 1, important parameters and test results of examples 1 to 32 and comparative examples 1 to 12
The result shows that the laser with the wavelength range of 190-1064nm is used for activating the resin composition containing the molybdenum sensitization auxiliary agent, the activation effect is good, and the electroless plating layer can be well carried out on the surface of the resin composition.
The molybdenum-containing sensitization auxiliary agent has low price, and can obviously reduce the production cost of the selectively metallized product capable of being activated by laser; and under the condition that the addition amount of the molybdenum-containing sensitization auxiliary is as low as 1 weight percent, the thickness of a coating of the obtained resin composition reaches more than 1.8 mu m, and the strength of the coating reaches the highest level of 5B when tested by a hundred-grid knife (ASTMD 3359), so that the resin composition is very suitable for industrial production and application.
In summary, the invention provides the application of the molybdenum-containing sensitization auxiliary in preparing the laser-activated selectively-metallized resin composition, and a resin composition capable of being selectively metallized by laser activation and a laser-activatable resin product with excellent further electroless plating effect. The inventors of the present invention have unexpectedly found that electroless copper plating can be performed well on the surface of a resin composition containing a molybdenum-containing sensitizing assistant added thereto by activation with a laser having a wavelength of 190 to 1064 nm. On the one hand, 190-1064nm covers almost all laser wavelengths, and activating the resin composition at different laser wavelengths can exert the advantages of the laser wavelengths themselves; on the other hand, compared with the traditional sensitization auxiliary containing copper, tin and bismuth, the molybdenum-containing sensitization auxiliary has lower price, and can obviously reduce the production cost. The invention can obtain the resin composition with excellent coating thickness and coating strength under the condition of lower molybdenum-containing sensitization auxiliary addition amount, and has excellent industrial application value.
Claims (10)
1. The application of the molybdenum-containing sensitization auxiliary in the laser activation selective metallization process of the resin composition is characterized in that: the molybdenum-containing sensitization auxiliary agent is selected from any one or more than two of molybdenum oxides, molybdenum sulfides, molybdenum hydroxides and molybdenum-containing acids, wherein the molybdenum oxides are selected from any one or more than two of molybdenum trioxide, molybdenum dioxide, iron-doped molybdenum oxide, molybdenum aluminum oxide and molybdenum zinc oxide, the molybdenum sulfides are molybdenum disulfide, the molybdenum hydroxides are molybdenum hydroxides, and the molybdenum-containing acids are any one or two of molybdic acid and phosphomolybdic acid; the laser activation is carried out by utilizing 190-1064nm wavelength laser;
the molybdenum-containing sensitization auxiliary agent and the polymer form a resin composition according to the following weight percentage: 1.0 to 55 percent of molybdenum-containing sensitization auxiliary agent and 45 to 99 percent of polymer.
2. The use according to claim 1, wherein: the resin composition comprises the following components in percentage by weight: 2-50% of molybdenum-containing sensitization auxiliary agent and 50-98% of polymer.
3. The use according to claim 2, wherein: the resin composition comprises the following components in percentage by weight: 10-50% of molybdenum-containing sensitization auxiliary agent and 50-90% of polymer.
4. The use according to claim 1, wherein: the average particle size of the molybdenum-containing sensitization auxiliary is less than or equal to 150 mu m.
5. The use according to claim 4, wherein: the average grain diameter of the molybdenum-containing sensitization auxiliary is 0.010 mu m-50 mu m.
6. The use according to claim 5, wherein: the average particle diameter of the molybdenum-containing sensitization auxiliary is 0.05-20 mu m.
7. The use according to claim 1, wherein: the polymer is selected from any one or more than two of polycarbonate, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyamide, polystyrene, K resin, PEN, polyphenyl ether, polyphenylene sulfide, polyether ether ketone, polyurethane, nylon elastomer, SEBS, SEPS, SEEPS and polyester elastomer.
8. The use according to claim 1, wherein: the preparation method of the resin composition comprises the following steps:
a. taking a molybdenum-containing sensitization auxiliary agent and a polymer, and uniformly mixing to obtain a mixture;
b. and d, carrying out melt blending and granulation on the mixture obtained in the step a to obtain the resin composition.
9. A method of preparing a microcircuit material, characterized by: the method is characterized in that the resin composition in any one of claims 1-8 is selectively activated under the laser with the wavelength of 190-1064nm, and then is subjected to electroless plating, so that the conductive metal is deposited in an activated area.
10. The method of claim 9, wherein: the conductive metal is copper, nickel or gold.
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