CN114450347A - Thermoplastic resin composition for laser direct structuring process and molded article including the same - Google Patents
Thermoplastic resin composition for laser direct structuring process and molded article including the same Download PDFInfo
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- CN114450347A CN114450347A CN202080067106.7A CN202080067106A CN114450347A CN 114450347 A CN114450347 A CN 114450347A CN 202080067106 A CN202080067106 A CN 202080067106A CN 114450347 A CN114450347 A CN 114450347A
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- resin composition
- thermoplastic resin
- bis
- weight
- maleic anhydride
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- 239000011342 resin composition Substances 0.000 title claims abstract description 78
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims description 14
- 238000007747 plating Methods 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 34
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 29
- 230000000996 additive effect Effects 0.000 claims abstract description 29
- 239000010452 phosphate Substances 0.000 claims abstract description 29
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 27
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 27
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 26
- 229920001225 polyester resin Polymers 0.000 claims abstract description 24
- 239000004645 polyester resin Substances 0.000 claims abstract description 24
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 239000010949 copper Substances 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 14
- 239000007924 injection Substances 0.000 claims description 14
- 238000009713 electroplating Methods 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 239000002905 metal composite material Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 229910052596 spinel Inorganic materials 0.000 claims description 7
- 239000011029 spinel Substances 0.000 claims description 7
- 238000007334 copolymerization reaction Methods 0.000 claims description 6
- 150000001879 copper Chemical class 0.000 claims description 5
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 description 23
- 239000010410 layer Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- -1 aromatic diol compound Chemical class 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 3
- WCMHCPWEQCWRSR-UHFFFAOYSA-J dicopper;hydroxide;phosphate Chemical compound [OH-].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O WCMHCPWEQCWRSR-UHFFFAOYSA-J 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 229910000153 copper(II) phosphate Inorganic materials 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- HNDVYGDZLSXOAX-UHFFFAOYSA-N 2,6-dichloro-4-propylphenol Chemical compound CCCC1=CC(Cl)=C(O)C(Cl)=C1 HNDVYGDZLSXOAX-UHFFFAOYSA-N 0.000 description 1
- WRLVTKZXVVEUPL-UHFFFAOYSA-N 2-chloro-4-propylphenol Chemical compound CCCC1=CC=C(O)C(Cl)=C1 WRLVTKZXVVEUPL-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- JZDUZYOTBVXERH-UHFFFAOYSA-N 4-[3-(4-hydroxyphenyl)-3-methylbut-1-enyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C=CC1=CC=C(O)C=C1 JZDUZYOTBVXERH-UHFFFAOYSA-N 0.000 description 1
- OAHMVZYHIJQTQC-UHFFFAOYSA-N 4-cyclohexylphenol Chemical compound C1=CC(O)=CC=C1C1CCCCC1 OAHMVZYHIJQTQC-UHFFFAOYSA-N 0.000 description 1
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910000604 Ferrochrome Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- KYPYTERUKNKOLP-UHFFFAOYSA-N Tetrachlorobisphenol A Chemical compound C=1C(Cl)=C(O)C(Cl)=CC=1C(C)(C)C1=CC(Cl)=C(O)C(Cl)=C1 KYPYTERUKNKOLP-UHFFFAOYSA-N 0.000 description 1
- 229910010340 TiFe Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LAUIXFSZFKWUCT-UHFFFAOYSA-N [4-[2-(4-phosphonooxyphenyl)propan-2-yl]phenyl] dihydrogen phosphate Chemical compound C=1C=C(OP(O)(O)=O)C=CC=1C(C)(C)C1=CC=C(OP(O)(O)=O)C=C1 LAUIXFSZFKWUCT-UHFFFAOYSA-N 0.000 description 1
- JAQXDZTWVWLKGC-UHFFFAOYSA-N [O-2].[Al+3].[Fe+2] Chemical compound [O-2].[Al+3].[Fe+2] JAQXDZTWVWLKGC-UHFFFAOYSA-N 0.000 description 1
- QEFDIAQGSDRHQW-UHFFFAOYSA-N [O-2].[Cr+3].[Fe+2] Chemical compound [O-2].[Cr+3].[Fe+2] QEFDIAQGSDRHQW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- GSWGDDYIUCWADU-UHFFFAOYSA-N aluminum magnesium oxygen(2-) Chemical compound [O--].[Mg++].[Al+3] GSWGDDYIUCWADU-UHFFFAOYSA-N 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 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
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920006245 ethylene-butyl acrylate Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 1
- KEHCHOCBAJSEKS-UHFFFAOYSA-N iron(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Fe+2] KEHCHOCBAJSEKS-UHFFFAOYSA-N 0.000 description 1
- CUSDLVIPMHDAFT-UHFFFAOYSA-N iron(3+);manganese(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Fe+3].[Fe+3] CUSDLVIPMHDAFT-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- MFJNMOFNZSZVAP-UHFFFAOYSA-N magnesium chromium(3+) oxygen(2-) Chemical compound [O-2].[Mg+2].[Cr+3] MFJNMOFNZSZVAP-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
-
- 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
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemically Coating (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The thermoplastic resin composition of the present invention comprises: about 100 parts by weight of a polycarbonate resin; about 5 to about 55 parts by weight of a glycol-modified polyester resin having about 20 to about 100 mole% 1, 4-cyclohexanedimethanol, relative to the total moles of the glycol component; about 0.5 to about 15 parts by weight of an additive for laser direct structuring; about 1 to about 10 parts by weight of a maleic anhydride-modified olefinic copolymer; and about 1 to about 10 parts by weight of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate, wherein the weight ratio of the additive for laser direct structuring to resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate is about 1:0.08 to about 1: 7. The thermoplastic resin composition is excellent in plating reliability, impact resistance, fluidity and the like.
Description
Technical Field
The present invention relates to a thermoplastic resin composition for laser direct structuring and a molded article comprising the same. More particularly, the present invention relates to a thermoplastic resin composition for laser direct structuring, which exhibits good characteristics in terms of plating reliability, impact resistance, flowability, and the like, and a molded article including the same.
Background
A Laser Direct Structuring (LDS) process may be used to form a metal layer on at least a portion of the surface of a molded article produced from the thermoplastic resin composition. The LDS process refers to a process of modifying a plating target area on the surface of a molded article to have characteristics suitable for plating by irradiating the plating target area with a laser beam. For this reason, the thermoplastic resin composition needs to contain an additive for laser direct structuring (LDS additive) which can form a metal core upon irradiation with a laser beam. The LDS additive is decomposed to produce a metal core. Further, the area irradiated with the laser beam has a rough surface. Due to this metal core and surface roughness, the laser modified region becomes suitable for electroplating.
The LDS process allows for rapid and economical formation of electronic/circuitry on three-dimensional molded articles. For example, the LDS process may be advantageously used to manufacture antennas for portable electronic devices, Radio Frequency Identification (RFID) antennas, and the like.
In recent years, with an increase in the trend of weight and thickness reduction of portable equipment devices, there has been an increasing demand for thermoplastic resin compositions that can exhibit excellent mechanical properties and molding processability (flowability). Further, as the thickness of a fine pattern (plating area) of an electric/electronic circuit such as a portable electronic device or the like becomes thinner, there may be a problem that plating reliability is deteriorated due to plating peeling.
Therefore, there is a need to develop a thermoplastic resin composition for laser direct structuring, which exhibits good properties in terms of plating reliability, impact resistance, flowability, and the like, and a molded article including the same.
Background art of the present invention is disclosed in korean patent laid-open publication No. 2011-0018319 and the like.
Disclosure of Invention
Technical problem
An object of the present invention is to provide a thermoplastic resin composition for laser direct structuring, which exhibits good characteristics in terms of plating reliability, impact resistance, flowability, and the like.
It is another object of the present invention to provide a molded article produced from the thermoplastic resin composition.
The above and other objects of the present invention will become apparent from the detailed description of the present invention.
Technical scheme
1. One aspect of the present invention relates to a thermoplastic resin composition. The thermoplastic resin composition comprises: about 100 parts by weight of a polycarbonate resin; about 5 to about 55 parts by weight of a glycol-modified polyester resin comprising about 20 to about 100 mole% 1, 4-cyclohexanedimethanol, based on the total moles of the glycol component; about 0.5 to about 15 parts by weight of an additive for laser direct structuring; about 1 to about 10 parts by weight of a maleic anhydride-modified olefin copolymer; and about 1 to about 10 parts by weight of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate, wherein the additive for laser direct structuring and the resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate may be present in a weight ratio of about 1:0.08 to about 1: 7.
2. In embodiment 1, the additive for laser direct structuring may include at least one of a heavy metal composite oxide spinel and a copper salt.
3. In embodiment 1 or 2, the maleic anhydride-modified olefin copolymer may include a maleic anhydride-modified alkylene- α -olefin copolymer obtained by graft copolymerization of maleic anhydride and an alkylene- α -olefin copolymer.
4. In embodiments 1 to 3, the maleic anhydride-modified olefin copolymer may include at least one of a maleic anhydride-modified ethylene-butene copolymer and a maleic anhydride-modified ethylene-octene copolymer.
5. In embodiments 1 to 4, the diol-modified polyester resin and the maleic anhydride-modified olefin copolymer may be present in a weight ratio of about 1:0.05 to about 1: 1.5.
6. In embodiments 1 to 5, the diol-modified polyester resin and resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate may be present in a weight ratio of about 1:0.03 to about 1: 1.5.
7. In embodiments 1 to 6, the maleic anhydride-modified olefin copolymer and resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate may be present in a weight ratio of about 1:0.2 to about 1: 7.
8. In embodiments 1 to 7, an injection-molded sample having a size of 50mm × 90mm × 3.2mm is left at 25 ℃ for 6 hours, the surface of the sample is activated in the form of stripes by laser direct structuring, a copper layer having a thickness of 35 μm is formed on the activated surface of the sample by electroplating (electroless copper plating), the sample is left in a chamber at 85 ℃ and 85% RH (relative humidity) for 120 hours, and after 100 meshes each having a size of 1mm × 1mm are engraved on the electroplated layer (copper layer), when an adhesive tape is attached to the sample and then peeled off from the sample, the thermoplastic resin composition may have about 92 to about 100 meshes which remain without being peeled off.
9. In embodiments 1 to 8, the thermoplastic resin composition may have a notched Izod impact strength of about 15kgf cm/cm to about 30kgf cm/cm when measured on a sample 1/8 ″ thick in accordance with ASTM D256.
10. In embodiments 1 to 9, when the molding temperature is 320 ℃, the mold temperature is 60 ℃,1,500 kgf/cm2Is measured after injection in a spiral mold having dimensions of 15mm wide and 1mm thick under the conditions of injection pressure and injection rate of 120mm/s, the thermoplastic resinThe composition may have a spiral flow length of about 280mm to about 350 mm.
11. Another aspect of the invention relates to a molded article. The molded article may be produced from the thermoplastic resin composition according to any one of embodiments 1 to 10.
12. In embodiment 11, the molded article may include a metal layer formed on at least a portion of a surface thereof by a laser direct structuring process and electroplating.
Advantageous effects
The present invention provides a thermoplastic resin composition for laser direct structuring, which exhibits good characteristics in terms of plating reliability, impact resistance, flowability, and the like, and a molded article produced therefrom.
Drawings
Fig. 1 is a schematic cross-sectional view of a molded article according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The thermoplastic resin composition according to the present invention is suitable for a laser direct structuring process (LDS process) and comprises: (A) a polycarbonate resin; (B) a diol-modified polyester resin; (C) additives for laser direct structuring (LDS additives); (D) maleic anhydride-modified olefin copolymers; and (E) resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate.
The expression "a to b" as used herein to denote a particular numerical range is defined as ". gtoreq.a.ltoreq.b".
(A) Polycarbonate resin
The polycarbonate resin according to an embodiment of the present invention may be selected from any polycarbonate resins used in typical thermoplastic resin compositions. For example, the polycarbonate resin may be an aromatic polycarbonate resin prepared by reacting a diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, carbonate diester, and the like.
In some embodiments, the diphenols may include, for example, 4, 4' -biphenol, 2-bis (4-hydroxyphenyl) propane, 2, 4-bis (4-hydroxyphenyl) -2-methylbutene, 1-bis (4-hydroxyphenyl) cyclohexane, 2-bis (3-chloro-4-hydroxyphenyl) propane, and 2, 2-bis- (3, 5-dichloro-4-hydroxyphenyl) propane, but are not limited thereto. For example, the diphenol may be 2, 2-bis (4-hydroxyphenyl) propane, 2-bis (3, 5-dichloro-4-hydroxyphenyl) propane or 1, 1-bis (4-hydroxyphenyl) cyclohexane, in particular 2, 2-bis (4-hydroxyphenyl) propane, which is also known as bisphenol-a.
In some embodiments, the polycarbonate resin may be a branched polycarbonate resin. For example, the polycarbonate resin may be a polycarbonate resin prepared by adding a trivalent or higher polyfunctional compound, particularly a trivalent or higher phenolic group-containing compound (in an amount of about 0.05 mol% to about 2 mol% based on the total moles of diphenols used in the polymerization).
In some embodiments, the polycarbonate resin may be a homopolycarbonate resin, a copolycarbonate resin, or a blend thereof. In addition, the polycarbonate resin may be partially or completely replaced by an aromatic polyester-carbonate resin (obtained by polymerization in the presence of an ester precursor, such as a difunctional carboxylic acid).
In some embodiments, the polycarbonate resin may have a weight average molecular weight (Mw) of about 10,000g/mol to about 200,000g/mol, for example, about 15,000g/mol to about 80,000g/mol, as measured by Gel Permeation Chromatography (GPC). Within this range, the thermoplastic resin composition may have good flowability (processability).
(B) Diol-modified polyester resin
According to the present invention, the glycol-modified polyester resin is used together with the maleic anhydride-modified olefin copolymer and the specific phosphate ester compound to improve plating reliability, impact resistance, flowability, etc. of the thermoplastic resin composition for laser direct structuring, and may be a glycol-modified polyester resin containing 1, 4-cyclohexanedimethanol in an amount of about 20 to about 100 mol% based on the total moles of the glycol component.
In some embodiments, the glycol-modified polyester resin may be modified by a dicarboxylic acid comprising terephthalic acid and a glycol component comprising about 20 mole% to about 100 mole%, for example, about 35 mole% to about 100 mole% 1, 4-Cyclohexanedimethanol (CHDM) and optionallyAbout 80 mol% or less, for example, about 65 mol% or less of C2To C6Alkylene glycol) by polycondensation. Within this range, the thermoplastic resin composition can exhibit good plating reliability, flowability, and the like.
In some embodiments, the glycol-modified polyester resin may have an intrinsic viscosity of about 0.5dl/g to about 0.8dl/g, for example, about 0.55dl/g to about 0.75dl/g, when measured in an o-chlorophenol solution (concentration: 1.2g/dl) at 35 ℃. Within this range, the thermoplastic resin composition may improve the miscibility between its components and may have good characteristics in mechanical characteristics, molding processability (flowability), and the like.
In some embodiments, the diol-modified polyester resin may be present in an amount of about 5 parts by weight to about 55 parts by weight, for example, about 5 parts by weight to about 50 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the diol-modified polyester resin is less than about 5 parts by weight relative to about 100 parts by weight of the polycarbonate resin, the thermoplastic resin composition may suffer from deterioration in plating reliability and the like, and if the content of the diol-modified polyester resin exceeds about 55 parts by weight, the thermoplastic resin composition may suffer from deterioration in plating reliability and the like.
(C) Additive for laser direct structuring
According to the present invention, the LDS additive is used to form a metal core upon irradiation with a laser beam, and may include any LDS additive used in a typical resin composition for LDS. Here, the laser beam means light amplified by simulated emission (simulated emission light), and may be UV light having a wavelength of about 100nm to about 400nm, visible light having a wavelength of about 400nm to about 800nm, or Infrared (IR) light having a wavelength of about 800nm to about 25,000nm, for example, IR light having a wavelength of about 1,000nm to about 2,000 nm.
In some embodiments, the LDS additive may include a heavy metal composite oxide spinel and/or a copper salt.
In some embodiments, the heavy metal composite oxide spinel may be represented by formula 1.
AB2O4
In formula 1, a is a metal cation having a valence of 2, for example, magnesium, copper, cobalt, zinc, tin, iron, manganese, nickel, and a combination thereof, and B is a metal cation having a valence of 3, for example, manganese, nickel, copper, cobalt, tin, titanium, iron, aluminum, chromium, and a combination thereof.
In the heavy metal composite oxide spinel represented by formula 1, a provides a monovalent cation component of the metal oxide cluster and B provides a monovalent cation component of the metal cation cluster. For example, the metal oxide cluster including a may have a tetrahedral structure and the metal oxide cluster including B may have an octahedral structure. Specifically, the heavy metal composite oxide spinel represented by formula 1 may have a structure in which: wherein the oxygen atoms are arranged in a cubic close-packed lattice and B and a occupy octahedral and tetrahedral sites in the lattice, respectively.
In some embodiments, the heavy metal composite oxide spinel may include magnesium aluminum oxide (MgAl)2O4) Zinc aluminum oxide (ZnAl)2O4) Iron aluminum oxide (FeAl)2O4) Copper iron oxide (CuFe)2O4) Copper chromium oxide (CuCr)2O4) Manganese iron oxide (MnFe)2O4) Nickel iron oxide (NiFe)2O4) Titanium iron oxide (TiFe)2O4) Iron chromium oxide (FeCr)2O4) Magnesium chromium oxide (MgCr)2O4) And combinations thereof. For example, the heavy metal complex oxide may be copper chromium oxide (CuCr)2O4). Copper chromium oxide (CuCr)2O4) Has a dark color and is therefore advantageous when the final molded article needs to be black or gray.
In some embodiments, the copper salt may include, but is not limited to, copper hydroxide phosphate, copper sulfate, cuprous thiocyanate, and combinations thereof. For example, the copper salt may be a copper hydroxide phosphate. Copper hydroxide phosphate is a compound in which copper phosphate is combined with copper hydroxide, and may include Cu3(PO4)2·2Cu(OH)2、Cu3(PO4)2·Cu(OH)2And the like. As additives, basicCopper phosphate does not affect the color reproduction characteristics of the colorant, and thus allows a molded article having a desired color to be easily obtained.
In some embodiments, the LDS additive can have an average particle size of about 0.01 μm to about 50 μm, for example, about 0.1 μm to about 30 μm, specifically about 0.5 μm to about 10 μm. Within this range, the LDS additive is capable of forming a uniform coating surface by laser direct structuring. As used herein, unless otherwise specifically stated, the term "average particle diameter" refers to D50 (diameter at 50% distribution) as the number average particle diameter.
In some embodiments, the LDS additive can be present in an amount of about 0.5 parts by weight to about 15 parts by weight, for example, about 1 part by weight to about 15 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the LDS additive is less than about 0.5 parts by weight relative to about 100 parts by weight of the polycarbonate resin, a sufficient amount of metal nuclei is not formed in the coating layer during irradiation of the thermoplastic resin composition (molded article) with a laser beam, resulting in deterioration of plating adhesion, and if the content of the LDS additive exceeds about 15 parts by weight, the thermoplastic resin composition may suffer from deterioration in impact resistance and heat resistance.
(D) Maleic anhydride-modified olefin copolymer
The maleic anhydride-modified olefin copolymer according to one embodiment of the present invention is a reactive olefin copolymer obtained by graft copolymerization of maleic anhydride, which is a reactive functional group, with an olefin copolymer, and is used to improve plating reliability, impact resistance and flowability of a thermoplastic resin composition together with a specific phosphate compound.
In some embodiments, the maleic anhydride-modified olefin copolymer may be obtained by graft copolymerization of maleic anhydride and an olefin copolymer obtained by copolymerization of at least two alkylene monomers. The alkylene monomer may be C2To C10Alkylene and may be selected from, for example, ethylene, propylene, isopropene, butene, isobutylene, octene, and combinations thereof.
In some embodiments, the maleic anhydride-modified olefin copolymer may include a maleic anhydride-modified alkylene- α -olefin copolymer obtained by graft copolymerization of maleic anhydride and an alkylene- α -olefin copolymer.
In some embodiments, the maleic anhydride modified olefin copolymer may include maleic anhydride modified ethylene-butene copolymers, maleic anhydride modified ethylene-octene copolymers, and combinations thereof.
In some embodiments, the maleic anhydride modified olefin copolymer may have a melt flow index of from about 0.5g/10min to about 20g/10min, for example, from about 1g/10min to about 10g/10min, when measured at 190 ℃ and 2.16kgf according to ASTM D1238.
In some embodiments, the maleic anhydride-modified olefin copolymer may be present in an amount of about 1 part by weight to about 10 parts by weight, for example, about 2 parts by weight to about 9 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of the maleic anhydride-modified olefin copolymer is less than about 1 part by weight with respect to about 100 parts by weight of the polycarbonate resin, the thermoplastic resin composition may suffer from deterioration in plating reliability and the like, and if the content of the maleic anhydride-modified olefin copolymer exceeds about 10 parts by weight, the thermoplastic resin composition may suffer from deterioration in impact resistance, flowability and the like.
In some embodiments, the glycol-modified polyester resin (B) and the maleic anhydride-modified olefin copolymer (D) may be present in a weight ratio (B: D) of about 1:0.05 to about 1:1.5, for example, about 1:0.1 to about 1:1. Within this range, the thermoplastic resin composition may exhibit good characteristics in terms of plating reliability, impact resistance, flowability, and the like.
(E) Resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate
According to the present invention, a phosphite compound is used to improve plating reliability, impact resistance and flowability of a thermoplastic resin composition for laser direct structuring, together with a glycol-modified polyester resin and a maleic anhydride-modified olefin copolymer.
In some embodiments, the resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate may be present in an amount of about 1 part by weight to about 10 parts by weight, for example, about 2 parts by weight to about 9 parts by weight, relative to about 100 parts by weight of the polycarbonate resin. If the content of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate is less than about 1 part by weight relative to about 100 parts by weight of the polycarbonate resin, the thermoplastic resin composition may suffer from deterioration in flowability and the like, and if the content of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate exceeds about 10 parts by weight, the thermoplastic resin composition may suffer from deterioration in flowability and the like.
In some embodiments, the additive (C) for laser direct structuring and the resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (E) may be present in a weight ratio (C: E) of about 1:0.08 to about 1:7, e.g., about 1:0.1 to about 1: 5. If the weight ratio of the additive for laser direct structuring to resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate is less than about 1:0.08, the thermoplastic resin composition may suffer from deterioration in plating reliability, flowability, and the like, and if the weight ratio thereof exceeds about 1:7, the thermoplastic resin composition may suffer from deterioration in flowability, and the like.
In some embodiments, the diol-modified polyester resin (B) and resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (E) may be present in a weight ratio (B: E) of about 1:0.03 to about 1:5, e.g., about 1:0.05 to about 1:1. Within this range, the thermoplastic resin composition can exhibit good characteristics in terms of plating reliability, fluidity, and the like.
In some embodiments, the maleic anhydride-modified olefin copolymer (D) and resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (E) may be present in a weight ratio (D: E) of about 1:0.2 to about 1:7, e.g., about 1:0.2 to about 1: 5. Within this range, the thermoplastic resin composition may exhibit good characteristics in terms of impact resistance, flowability, and the like.
In some embodiments, the thermoplastic resin composition may further include any additives commonly used in typical thermoplastic resin compositions. Examples of the additives may include inorganic fillers, flame retardants, anti-dripping agents, lubricants, nucleating agents, stabilizers, mold release agents, pigments, dyes, and mixtures thereof, but are not limited thereto. The additive may be present in an amount of about 0.001 parts by weight to about 40 parts by weight, for example, about 0.1 parts by weight to about 10 parts by weight, relative to about 100 parts by weight of the polycarbonate resin.
According to one embodiment, the thermoplastic resin composition may be prepared in pellet form by mixing the above components and then melt extruding the mixture in a typical double rod extruder at about 200 ℃ to about 280 ℃, for example about 220 ℃ to about 260 ℃.
In some embodiments, an injection molded sample having a size of 50mm × 90mm × 3.2mm is left at 25 ℃ for 6 hours, the surface of the sample is activated in a stripe form by laser direct structuring, a 35 μm thick copper layer is formed on the activated surface of the sample by electroplating (electroless copper plating), the sample is left in a chamber at 85 ℃ and 85% RH for 120 hours, and after 100 meshes each having a size of 1mm × 1mm are engraved on the electroplated layer (copper layer), when an adhesive tape is attached to and then peeled off from the sample, the thermoplastic resin composition may have about 92 to about 100 meshes, for example, about 95 to about 100 meshes that remain without being peeled off.
In some embodiments, the thermoplastic resin composition may have a notched Izod impact strength of about 15 kgf-cm/cm to about 30 kgf-cm/cm, for example, about 19 kgf-cm/cm to about 25 kgf-cm/cm, when measured on a sample 1/8 ″ thick in accordance with ASTM D256.
In some embodiments, when at a molding temperature of 320 ℃, a mold temperature of 60 ℃,1,500 kgf/cm2The thermoplastic resin composition may have a spiral flow length of about 280mm to about 350mm, for example, about 290 to about 340mm, when measured after injection in a spiral mold having dimensions of 15mm wide and 1mm thick under the conditions of injection pressure and injection rate of 120 mm/s.
The molded article according to the present invention can be produced from the thermoplastic resin composition according to the above. For example, the thermoplastic resin composition may be used to prepare a molded article by any suitable molding method, such as injection molding, compression molding, blow molding, extrusion molding, and the like. The molded article can be easily formed by those skilled in the art.
Fig. 1 is a schematic cross-sectional view of a molded article according to an embodiment of the present invention. It should be noted that the thickness of lines of the drawings or the size of components is exaggerated for convenience and clarity of description only. Referring to fig. 1, the molded article 10 according to this embodiment may include a metal layer 20 formed on at least a portion of a surface thereof by LDS and electroplating. The molded article 10 according to the embodiment may be a circuit carrier for manufacturing an antenna. For example, the molded article 10 may be manufactured by preparing the preform 10 by injection molding of a thermoplastic resin composition, and irradiating a specific region (a portion where the metal layer 20 is to be formed) on the surface of the preform 10 with a laser beam, followed by metallizing (plating) the irradiated region to form the metal layer 20.
In this embodiment, the LDS additive included in the preform 10 decomposes under laser beam irradiation to form metal nuclei. In addition, the laser beam irradiated region has a surface roughness suitable for plating. Here, the laser beam may have a wavelength of about 248nm, about 308nm, about 355nm, about 532nm, about 1,064nm, or about 10,600 nm.
In this embodiment, the metallization may be performed by any typical electroplating process. For example, metallization may include immersing the laser beam irradiated preform 10 in at least one electroless plating bath to form a metal layer 20 (conductive path) on the laser beam irradiated regions of the surface of the preform 10. Here, examples of electroless plating may include copper plating, gold plating, nickel plating, silver plating, zinc plating, and tin plating.
Those skilled in the art can readily produce molded articles having a metal layer on at least a portion of their surface by LDS.
Modes of the invention
Next, the present invention will be described in more detail with reference to some examples. It should be understood that these examples are provided for illustration only and are not to be construed as limiting the invention in any way.
Examples
The details of the components used in examples and comparative examples are as follows.
(A) Polycarbonate resin
A bisphenol-A type polycarbonate resin having a weight average molecular weight (Mw) of 25,000g/mol was used.
(B) Polyester resin
(B1) A diol-modified polyester resin containing 100 mol% of 1, 4-cyclohexanedimethanol based on the total moles of diol components (manufacturer: SK Chemicals, product name: SKYPURA 0302) was used.
(B2) Polyethylene terephthalate (manufacturer: SK Chemicals, product name: SKYPET1100) was used.
(C) Additive for laser direct structuring
Basic copper phosphate (manufacturer: Merck Performance Materials Co., Ltd.) was used.
(D) Modified olefin copolymer
(D1) Maleic anhydride-modified ethylene-octene copolymer (manufacturer: DuPont) was used.
(D2) An ethylene-butyl acrylate copolymer modified with glycidyl methacrylate (manufacturer: DuPont) was used.
(E) Phosphate ester compound
(E1) Resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (manufacturer: DAIHACHI, product name: PX-200) was used.
(E2) bisphenol-A diphosphate (manufacturer: DAIHACHI, product name: DVP506) was used.
Examples 1 to 9 and comparative examples 1 to 13
The above components were weighed in the amounts listed in tables 1 to 3, and extruded at 260 ℃ to prepare thermoplastic resin compositions in the form of pellets. The pellets thus prepared were dried at 100 ℃ for 4 hours or more by extrusion using a twin-screw extruder (L/D: 36,. phi.45 mm), and injection-molded using a 10 oz injection molding machine (injection temperature: 300 ℃) to prepare samples. The following properties of the prepared samples were evaluated by the following methods, and the evaluation results are shown in tables 1 to 3.
Evaluation of characteristics
(1) Electroplating reliability: an injection-molded sample having dimensions of 50mm × 90mm × 3.2mm was left at 25 ℃ for 6 hours, and then the surface of the sample was activated in the form of stripes by laser forming. Then, a 35 μm-thick copper layer was formed on the activated surface of the sample by electroplating (electroless copper plating), and left in the chamber at 85 ℃ and 85% RH for 120 hours, followed by engraving 100 meshes each having a size of 1mm × 1mm on the plating layer (copper layer), and then counting the number of meshes remaining on the plating layer when the tape was peeled off from the plating layer.
(2) Notched Izod impact resistance (kgf □ cm/cm): notched Izod impact strength was measured according to ASTM D256 on 1/8 "thick samples.
(3) Fluidity: at a molding temperature of 260 ℃, a mold temperature of 60 ℃,1,500 kgf/cm2Is injected in a spiral mold having dimensions of 15mm wide and 1mm thick, and the spiral flow length (unit: mm) is measured under the conditions of the injection pressure of (1) and the injection rate of 120 mm/s.
TABLE 1
TABLE 2
TABLE 3
As can be seen from the results, the thermoplastic resin composition according to the present invention has good characteristics in terms of plating reliability, impact resistance, fluidity, etc.
In contrast, it was seen that the thermoplastic resin composition prepared using an insufficient amount of the diol-modified polyester resin (comparative example 1) suffered deterioration in plating reliability and the like; the thermoplastic resin composition prepared using an excessive amount of the diol-modified polyester resin (comparative example 2) suffered from deterioration in plating reliability and the like; and the thermoplastic resin composition (comparative example 3) prepared using polyethylene terephthalate (B2) in place of the glycol-modified polyester resin of the present invention suffered from deterioration in plating reliability, impact resistance, and the like. It can be seen that the thermoplastic resin composition prepared using an insufficient amount of the additive for laser direct structuring (comparative example 4) suffered deterioration in plating reliability and the like; and the thermoplastic resin composition prepared using an excessive amount of the additive for laser direct structuring (comparative example 5) suffered from deterioration in plating reliability, impact resistance, and the like. It can be seen that the thermoplastic resin composition prepared using an insufficient amount of the maleic anhydride-modified olefin copolymer (comparative example 6) suffered from deterioration in impact resistance; the thermoplastic resin composition prepared using an excessive amount of the maleic anhydride-modified olefin copolymer (comparative example 7) suffered from deterioration in impact resistance, flowability, and the like; and the thermoplastic resin composition (comparative example 8) prepared using the glycidyl methacrylate-modified ethylene-butyl acrylate copolymer (D2) instead of the maleic anhydride-modified olefin copolymer suffered from deterioration in impact resistance and the like. It can be seen that the thermoplastic resin composition prepared using an insufficient amount of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (comparative example 9) suffers from deterioration in flowability and the like; the thermoplastic resin composition prepared using an excess amount of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (comparative example 10) suffered from deterioration in flowability and the like; and the thermoplastic resin composition prepared using bisphenol-a diphosphoric acid (E2) instead of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (comparative example 11) suffered from deterioration in flowability and the like. In addition, it can be seen that the thermoplastic resin composition (comparative example 12) prepared using the additive for laser direct structuring and resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate in a weight ratio smaller than that according to the present invention suffered from deterioration in plating reliability, flowability and the like; and the thermoplastic resin composition (comparative example 13) prepared using the additive for laser direct structuring and resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate in a weight ratio exceeding that according to the present invention suffered from deterioration in injection moldability and the like.
It is to be understood that various modifications, alterations, changes and equivalent embodiments may be made by those skilled in the art without departing from the spirit and scope of the invention.
Claims (12)
1. A thermoplastic resin composition comprising:
about 100 parts by weight of a polycarbonate resin;
about 5 to about 55 parts by weight, based on the total moles of the diol component, of a diol-modified polyester resin comprising about 20 to about 100 mole% 1, 4-cyclohexanedimethanol;
about 0.5 to about 15 parts by weight of an additive for laser direct structuring;
about 1 to about 10 parts by weight of a maleic anhydride-modified olefin copolymer; and
from about 1 to about 10 parts by weight of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate,
wherein the additive for laser direct structuring and the resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate are present in a weight ratio of about 1:0.08 to about 1: 7.
2. The thermoplastic resin composition of claim 1, wherein said additive for laser direct structuring comprises at least one of a heavy metal composite oxide spinel and a copper salt.
3. The thermoplastic resin composition of claim 1, wherein said maleic anhydride-modified olefin copolymer comprises a maleic anhydride-modified alkylene-a-olefin copolymer obtained by graft copolymerization of maleic anhydride and an alkylene-a-olefin copolymer.
4. The thermoplastic resin composition of claim 1, wherein said maleic anhydride-modified olefin copolymer comprises at least one of a maleic anhydride-modified ethylene-butene copolymer and a maleic anhydride-modified ethylene-octene copolymer.
5. The thermoplastic resin composition of claim 1, wherein said glycol-modified polyester resin and said maleic anhydride-modified olefin copolymer are present in a weight ratio of about 1:0.05 to about 1: 1.5.
6. The thermoplastic resin composition of claim 1, wherein said glycol-modified polyester resin and said resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate are present in a weight ratio of about 1:0.03 to about 1: 1.5.
7. The thermoplastic resin composition of claim 1, wherein said maleic anhydride modified olefin copolymer and said resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate are present in a weight ratio of about 1:0.2 to about 1: 7.
8. The thermoplastic resin composition as claimed in claim 1, wherein after an injection-molded sample having a size of 50mm x 90mm x 3.2mm is left at 25 ℃ for 6 hours, the surface of the sample is activated in the form of stripes by laser direct structuring, a 35 μm-thick copper layer is formed on the activated surface of the sample by electroplating (electroless copper plating), the sample is left in a chamber at 85 ℃ and 85% relative humidity for 120 hours, and after 100 meshes each having a size of 1mm x 1mm are engraved on the electroplated layer (copper layer), when an adhesive tape is attached to the injection-molded sample and then peeled off from the injection-molded sample, the thermoplastic resin composition has about 92 to about 100 meshes which remain without being peeled off.
9. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition has a notched izod impact strength of about 15 kgf-cm/cm to about 30 kgf-cm/cm when measured on a 1/8 "thick sample according to ASTM D256.
10. The thermoplastic resin composition of claim 1, wherein when at a molding temperature of 320 ℃, a mold temperature of 60 ℃,1,500 kgf/cm2Under the conditions of injection pressure and injection rate of 120mm/s, underThe thermoplastic resin composition has a spiral flow length of from about 280mm to about 350mm when measured after injection in a spiral mold having dimensions of 15mm wide and 1mm thick.
11. A molded article produced from the thermoplastic resin composition according to any one of claims 1 to 10.
12. The molded article of claim 11, wherein the molded article comprises a metal layer formed on at least a portion of a surface thereof by a laser direct structuring process and electroplating.
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| KR1020190120391A KR102340429B1 (en) | 2019-09-30 | 2019-09-30 | Thermoplastic resin composition for laser direct structuring process and article comprising the same |
| KR10-2019-0120391 | 2019-09-30 | ||
| PCT/KR2020/008905 WO2021066297A1 (en) | 2019-09-30 | 2020-07-08 | Thermoplastic resin composition for laser direct structuring process and molded article comprising same |
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| CN114450347A true CN114450347A (en) | 2022-05-06 |
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| CN202080067106.7A Active CN114450347B (en) | 2019-09-30 | 2020-07-08 | Thermoplastic resin composition for laser direct structuring process and molded article comprising the same |
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| KR (1) | KR102340429B1 (en) |
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| WO (1) | WO2021066297A1 (en) |
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| KR20150078277A (en) * | 2013-12-30 | 2015-07-08 | 제일모직주식회사 | Flame retardant thermoplastic resin composition and article comprising the same |
| CN104937032A (en) * | 2012-09-17 | 2015-09-23 | 沙特基础全球技术有限公司 | Laser direct structuring materials with improved plating performance and acceptable mechanical properties |
| KR20180070132A (en) * | 2016-12-16 | 2018-06-26 | 롯데첨단소재(주) | Thermoplastic resin composition for laser direct structuring process and article comprising the same |
| CN110003564A (en) * | 2017-12-26 | 2019-07-12 | 现代自动车株式会社 | Polypropylene resin composite for laser welding and the molding product for vehicle including it |
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| US20020134771A1 (en) * | 2001-01-05 | 2002-09-26 | Richard Wenger | Flame-retarded laser-markable polyester composition |
| US8492464B2 (en) * | 2008-05-23 | 2013-07-23 | Sabic Innovative Plastics Ip B.V. | Flame retardant laser direct structuring materials |
| US20150069290A1 (en) * | 2013-09-10 | 2015-03-12 | Sabic Innovative Plastics Ip B.V. | Polycarbonate based ductile thermally conductive polymer compositions and uses |
| KR101806597B1 (en) * | 2014-12-24 | 2018-01-11 | 롯데첨단소재(주) | Thermoplastic resin composition for laser direct structuring and molded article using thereof |
| KR102230830B1 (en) * | 2017-12-12 | 2021-03-23 | 롯데첨단소재(주) | Thermoplastic resin composition for laser direct structuring process and article comprising the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104937032A (en) * | 2012-09-17 | 2015-09-23 | 沙特基础全球技术有限公司 | Laser direct structuring materials with improved plating performance and acceptable mechanical properties |
| KR20150078277A (en) * | 2013-12-30 | 2015-07-08 | 제일모직주식회사 | Flame retardant thermoplastic resin composition and article comprising the same |
| KR20180070132A (en) * | 2016-12-16 | 2018-06-26 | 롯데첨단소재(주) | Thermoplastic resin composition for laser direct structuring process and article comprising the same |
| CN108203540A (en) * | 2016-12-16 | 2018-06-26 | 乐天尖端材料株式会社 | Thermoplastic resin composition for laser direct forming technique and the product containing it |
| CN110003564A (en) * | 2017-12-26 | 2019-07-12 | 现代自动车株式会社 | Polypropylene resin composite for laser welding and the molding product for vehicle including it |
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| Publication number | Publication date |
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| WO2021066297A1 (en) | 2021-04-08 |
| KR102340429B1 (en) | 2021-12-16 |
| CN114450347B (en) | 2024-03-29 |
| KR20210037906A (en) | 2021-04-07 |
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