CN114450347B - Thermoplastic resin composition for laser direct structuring process and molded article comprising the same - Google Patents
Thermoplastic resin composition for laser direct structuring process and molded article comprising the same Download PDFInfo
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- CN114450347B CN114450347B CN202080067106.7A CN202080067106A CN114450347B CN 114450347 B CN114450347 B CN 114450347B CN 202080067106 A CN202080067106 A CN 202080067106A CN 114450347 B CN114450347 B CN 114450347B
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- resin composition
- thermoplastic resin
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- 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
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 38
- 239000000654 additive Substances 0.000 claims abstract description 34
- 230000000996 additive effect Effects 0.000 claims abstract description 31
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 239000010452 phosphate Substances 0.000 claims abstract description 28
- 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 25
- 229920001225 polyester resin Polymers 0.000 claims abstract description 24
- 239000004645 polyester resin Substances 0.000 claims abstract description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 8
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims abstract description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 21
- 239000010949 copper Substances 0.000 claims description 17
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 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 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 238000000465 moulding Methods 0.000 claims description 11
- 238000009713 electroplating Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 7
- 239000002905 metal composite material Substances 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
- 238000007747 plating Methods 0.000 abstract description 43
- 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
- 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 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
- 125000002947 alkylene group Chemical group 0.000 description 4
- 239000008188 pellet 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
- 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000002245 particle 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 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
- 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 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229940106691 bisphenol a Drugs 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
- 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
- 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
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 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
- 229910001200 Ferrotitanium 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
- 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
- 230000003213 activating effect 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-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
- 238000000071 blow moulding Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- BQVVSSAWECGTRN-UHFFFAOYSA-L copper;dithiocyanate Chemical compound [Cu+2].[S-]C#N.[S-]C#N BQVVSSAWECGTRN-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
- 150000002009 diols Chemical class 0.000 description 1
- 238000001035 drying Methods 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
- 239000003063 flame retardant Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000014509 gene expression Effects 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
- 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
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- 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 parts by weight to about 55 parts by weight of a glycol-modified polyester resin having about 20mol% to about 100mol% of 1, 4-cyclohexanedimethanol, relative to the total moles of the glycol component; about 0.5 parts by weight 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 weight ratio of the additive for laser direct structuring to resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate is from about 1:0.08 to about 1:7. The thermoplastic resin composition has excellent plating reliability, impact resistance, fluidity, etc.
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 comprising the same.
Background
A Laser Direct Structuring (LDS) process may be used to form a metal layer on at least part 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 when irradiated with a laser beam. The LDS additive is decomposed to produce metal nuclei. Furthermore, the area irradiated with the laser beam has a rough surface. Due to such metal nuclei and surface roughness, the laser modified region becomes suitable for electroplating.
The LDS process allows for the rapid and economical formation of electronic/electrical circuits 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 the increasing trend of weight and thickness reduction of portable equipment devices, there has been an increasing demand for thermoplastic resin compositions which can exhibit excellent mechanical properties and molding processability (flowability). Further, as the thickness of fine patterns (plating areas) of an electric/electronic circuit such as a portable electronic device or the like becomes thin, there may be a problem in 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 comprising the same.
The background art of the present invention is disclosed in korean patent laid-open publication No. 2011-0018319, etc.
Disclosure of Invention
Technical problem
The 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, fluidity, and the like.
It is another object of the present invention to provide molded articles 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 proposal
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 parts by weight to about 55 parts by weight of a glycol-modified polyester resin containing about 20mol% to about 100mol% of 1, 4-cyclohexanedimethanol based on the total moles of the glycol component; about 0.5 parts by weight 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 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 glycol 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 glycol-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 from about 1:0.2 to about 1:7.
8. In embodiments 1 to 7, after an injection molded sample having dimensions of 50mm×90mm×3.2mm is placed at 25 ℃ for 6 hours, the surface of the sample is activated in the form of stripes by laser direct molding, a 35 μm thick copper layer is formed on the activated surface of the sample by electroplating (electroless copper plating), the sample is placed in a chamber at 85 ℃ and 85% rh (relative humidity) for 120 hours, and 100 grids each having dimensions of 1mm×1mm are engraved on an electroplated layer (copper layer), the thermoplastic resin composition may have about 92 to about 100 grids which remain without being peeled off when an adhesive tape is attached to the sample and then peeled off from the sample.
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, as measured on a 1/8' thick sample according to ASTM D256.
10. In embodiments 1 to 9, when at a molding temperature of 320 ℃, a mold temperature of 60 ℃,1,500 kgf/cm 2 The thermoplastic resin composition may have a helical flow length of about 280mm to about 350mm as measured after injection molding in a helical mold having dimensions 15mm wide and 1mm thick under injection pressure and an injection rate of 120 mm/s.
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, etc., 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 includes: (A) a polycarbonate resin; (B) a glycol-modified polyester resin; (C) Additives for laser direct structuring (LDS additives); (D) maleic anhydride modified olefin copolymer; and (E) resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate.
The expressions "a to b" used herein to represent specific numerical ranges are defined as ". Gtoreq.a and. Ltoreq.b".
(A) Polycarbonate resin
The polycarbonate resin according to an embodiment of the present invention may be selected from any polycarbonate resin used in a typical thermoplastic resin composition. For example, the polycarbonate resin may be an aromatic polycarbonate resin prepared by reacting diphenol (aromatic diol compound) with a precursor such as phosgene, halogen formate, carbonate diester, etc.
In some embodiments, diphenols may include, for example, 4' -diphenol, 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 valent polyfunctional compound, particularly a trivalent or higher valent phenol group-containing compound (in an amount of about 0.05mol% to about 2mol% 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) Glycol 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 compound to improve the plating reliability, impact resistance, flowability, etc. of the thermoplastic resin composition for laser direct structuring, and may be a glycol-modified polyester resin containing about 20mol% to about 100mol% of 1, 4-cyclohexanedimethanol based on the total mole number of the glycol component.
In some embodiments, the glycol-modified polyester resin may be prepared by reacting a dicarboxylic acid comprising terephthalic acid and a glycol component (comprising about 20mol% to about 100mol%, e.g., about 35mol% to about 100mol% 1, 4-Cyclohexanedimethanol (CHDM) and optionally about 80mol% or less, e.g., about 65mol% or less of C 2 To C 6 Alkylene glycol). Within this range, the thermoplastic resin composition may exhibit good plating reliability, fluidity, 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, as measured in an o-chlorophenol solution (concentration: 1.2 g/dl) at 35 ℃. Within this range, the thermoplastic resin composition can improve the miscibility between its components, and can have good characteristics in terms of mechanical properties, molding processability (flowability), and the like.
In some embodiments, the glycol-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 glycol-modified polyester resin is less than about 5 parts 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 glycol-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 when irradiated with a laser beam, and may include any LDS additive used in typical resin compositions for LDS. Here, the laser beam means light amplified by analog emission (analog 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 heavy metal composite oxide spinel and/or copper salts.
In some embodiments, the heavy metal composite oxide spinel may be represented by formula 1.
AB 2 O 4
In formula 1, a is a metal cation having a valence of 2, for example, magnesium, copper, cobalt, zinc, tin, iron, manganese, nickel, and combinations thereof, and B is a metal cation having a valence of 3, for example, manganese, nickel, copper, cobalt, tin, titanium, iron, aluminum, chromium, and combinations thereof.
In the heavy metal composite oxide spinel represented by formula 1, a provides a monovalent cation component of a metal oxide cluster and B provides a monovalent cation component of a 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 such a structure: wherein oxygen atoms are arranged in a cubic close-packed lattice and B and a occupy octahedral and tetrahedral sites, respectively, in the lattice.
In some embodiments, the heavy metal composite oxide spinel may include magnesia alumina (MgAl 2 O 4 ) Zinc aluminum oxide (ZnAl) 2 O 4 ) Iron aluminum oxide (FeAl) 2 O 4 ) Copper iron oxide (CuFe) 2 O 4 ) Copper chromium oxide (CuCr) 2 O 4 ) Manganese iron oxide (MnFe) 2 O 4 ) Nickel iron oxide (NiFe) 2 O 4 ) Ferrotitanium oxide (TiFe) 2 O 4 ) Iron chromium oxide (FeCr) 2 O 4 ) Magnesium chromium oxide (MgCr) 2 O 4 ) And combinations thereof. For example, the heavy metal complex oxide may be copper chromium oxide (CuCr 2 O 4 ). Copper chromium oxide (CuCr) 2 O 4 ) Has a dark colour and is therefore advantageous when the final moulded article needs to be black or grey.
In some embodiments, the copper salt may include, but is not limited to, basic copper phosphate, copper sulfate, copper thiocyanate, and combinations thereof. For example, the copper salt may be basic copper phosphate. Basic copper phosphate is a compound in which copper phosphate is combined with copper hydroxide, and may include Cu 3 (PO 4 ) 2 ·2Cu(OH) 2 、Cu 3 (PO 4 ) 2 ·Cu(OH) 2 Etc. As an additive, basic copper phosphate does not affect the color reproduction characteristics of the colorant, and thus allows molded articles having a desired color to be easily obtained.
In some embodiments, the LDS additive may 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 specifically stated otherwise, the term "average particle size" refers to D50 (diameter at 50% distribution) as the number average particle size.
In some embodiments, the LDS additive may 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 with respect 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 the 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 deterioration in impact resistance and heat resistance.
(D) Maleic anhydride modified olefin copolymer
The maleic anhydride-modified olefin copolymer according to an 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 with an olefin copolymer obtained by copolymerization of at least two alkylene monomers. The alkylene monomer may be C 2 To C 10 Alkylene groups and may be selected from, for example, ethylene, propylene, isobutylene, butene, isobutylene, octene, and combinations thereof.
In some embodiments, the maleic anhydride modified olefin copolymer may include a maleic anhydride modified alkylene-alpha-olefin copolymer obtained by graft copolymerization of maleic anhydride and an alkylene-alpha-olefin copolymer.
In some embodiments, the maleic anhydride modified olefin copolymer may include a maleic anhydride modified ethylene-butene copolymer, a maleic anhydride modified ethylene-octene copolymer, and combinations thereof.
In some embodiments, the maleic anhydride modified olefin copolymer may have a melt flow index of about 0.5g/10min to about 20g/10min, for example, about 1g/10min to about 10g/10min, when measured according to ASTM D1238 at 190 ℃ and 2.16 kgf.
In some embodiments, the maleic anhydride-modified olefin copolymer may be present in an amount of about 1 to about 10 parts by weight, for example, about 2 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, fluidity, and the like.
(E) Resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate
According to the present invention, a phosphite compound is used to improve the 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, resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate may be present in an amount of about 1 to about 10 parts by weight, for example, about 2 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 with respect to about 100 parts by weight of the polycarbonate resin, the thermoplastic resin composition may suffer from deterioration in terms of 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 terms of flowability and the like.
In some embodiments, the additive (C) and resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (E) for laser direct structuring may be present in a weight ratio (C: E) of about 1:0.08 to about 1:7, for example, 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 terms of plating reliability, flowability, etc., and if the weight ratio exceeds about 1:7, the thermoplastic resin composition may suffer from deterioration in terms of flowability, etc.
In some embodiments, the glycol-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, for example, about 1:0.05 to about 1:1. Within this range, the thermoplastic resin composition may 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 from about 1:0.2 to about 1:7, for example, from 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 additive 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 twin-screw extruder at a temperature of about 200 ℃ to about 280 ℃, for example about 220 ℃ to about 260 ℃.
In some embodiments, after placing an injection molded sample having dimensions of 50mm×90mm×3.2mm at 25 ℃ for 6 hours, activating the surface of the sample in the form of stripes by laser direct molding, forming a 35 μm thick copper layer on the activated surface of the sample by electroplating (electroless copper plating), placing the sample in a chamber at 85 ℃ and 85% rh for 120 hours, and engraving 100 grids each having dimensions of 1mm×1mm on the electroplated layer (copper layer), the thermoplastic resin composition may have about 92 to about 100 grids that remain without being peeled off when an adhesive tape is attached to and then peeled off from the sample.
In some embodiments, the thermoplastic resin composition may have a notched Izod impact strength of about 15kgf cm/cm to about 30kgf cm/cm, e.g., about 19kgf cm/cm to about 25kgf cm/cm, when measured on a 1/8' thick sample according to ASTM D256.
In some embodiments, the molding temperature is 1,500kgf/cm when at 320 ℃,60 ℃, mold temperature 2 The thermoplastic resin composition may have a helical flow length of about 280mm to about 350mm, for example, about 290 to about 340mm, as measured after injection molding in a helical mold having dimensions 15mm wide and 1mm thick under conditions of an injection pressure and an 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 molded articles by any suitable molding method, such as injection molding, compression molding, blow molding, extrusion molding, and the like. Molded articles can be readily 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 the lines of the drawings or the size of the components are exaggerated for descriptive convenience and clarity only. Referring to fig. 1, a 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, and then metallizing (plating) the irradiated region to form the metal layer 20.
In this embodiment, the LDS additive included in the pellet 10 is decomposed under irradiation of a laser beam to form a metal core. In addition, the laser beam irradiation region has a surface roughness suitable for electroplating. 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, the metallization may include immersing the laser beam irradiated patch 10 in at least one electroless plating bath to form a metal layer 20 (conductive path) on the laser beam irradiated area of the surface of the patch 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 manufacture molded articles having a metal layer on at least a portion of their surfaces by LDS.
Mode for the invention
Next, the present invention will be described in more detail with reference to some embodiments. 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
Details of the components used in the examples and comparative examples are as follows.
(A) Polycarbonate resin
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 (manufacturer: SK Chemicals, product name: SKYPERA 0302) containing 100mol% of 1, 4-cyclohexanedimethanol based on the total mole number of the diol component was used.
(B2) Polyethylene terephthalate (manufacturer: SK Chemicals, product name: SKYPET 1100) 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) Glycidyl methacrylate modified ethylene butyl acrylate copolymer (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: DVP 506) 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 sample was prepared by extrusion using a twin-rod extruder (L/d=36, Φ45 mm), drying the prepared pellets at 100 ℃ for 4 hours or more, and injection molding using a 10 oz injection molding machine (injection temperature: 300 ℃). The following properties of the prepared samples were evaluated by the following methods, and the evaluation results are shown in tables 1 to 3.
Characteristic evaluation
(1) Plating reliability: the 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 molding. 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 grids each having a size of 1mm×1mm on the plating layer (copper layer), followed by counting the number of grids 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 on 1/8' thick samples according to ASTM D256.
(3) Fluidity: at a molding temperature of 260 ℃, a mold temperature of 60 ℃,1,500 kgf/cm 2 Under the conditions of an injection pressure of 120mm/s and an injection rate of 15mm wide and 1mm thickAfter injection in a spiral mold, the spiral flow length (in mm) was measured.
TABLE 1
TABLE 2
TABLE 3 Table 3
From the results, it can be seen that the thermoplastic resin composition according to the present invention has good characteristics in terms of plating reliability, impact resistance, fluidity, and the like.
In contrast, it can be seen that the thermoplastic resin composition prepared using the insufficient amount of the glycol-modified polyester resin (comparative example 1) suffered from deterioration in plating reliability and the like; the thermoplastic resin composition (comparative example 2) prepared using the excessive amount of the diol-modified polyester resin suffered from deterioration in plating reliability and the like; and the thermoplastic resin composition (comparative example 3) prepared using polyethylene terephthalate (B2) instead of the diol-modified polyester resin of the present invention suffers 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 from deterioration in plating reliability and the like; and the thermoplastic resin composition (comparative example 5) prepared using an excessive amount of the additive for laser direct structuring suffered from deterioration in plating reliability, impact resistance, and the like. As can be seen, the thermoplastic resin composition prepared using the insufficient amount of the maleic anhydride-modified olefin copolymer (comparative example 6) suffered from deterioration in impact resistance; the thermoplastic resin composition prepared using the 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) suffered from deterioration in fluidity and the like; the thermoplastic resin composition prepared using an excessive amount of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (comparative example 10) suffered from deterioration in fluidity and the like; and the thermoplastic resin composition prepared using bisphenol-A diphosphate (E2) in place of resorcinol-bis (bis-2, 6-dimethylphenyl) phosphate (comparative example 11) suffered from deterioration in fluidity 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, etc.; 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 will be understood by those skilled in the art that various modifications, changes, variations and equivalent embodiments may be made without departing from the spirit and scope of the invention.
Claims (11)
1. A thermoplastic resin composition comprising:
100 parts by weight of a polycarbonate resin;
5 to 50 parts by weight of a glycol-modified polyester resin containing 20 to 100mol% of 1, 4-cyclohexanedimethanol based on the total mole number of the glycol component;
1 to 15 parts by weight of an additive for laser direct structuring;
1 to 10 parts by weight of a maleic anhydride-modified olefin copolymer; and
1 to 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 1:0.1 to 1:5,
wherein the additive for laser direct structuring comprises at least one of a heavy metal composite oxide spinel and a copper salt.
2. The thermoplastic resin composition of claim 1, wherein the 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.
3. The thermoplastic resin composition of claim 1, wherein the 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.
4. 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 1:0.05 to 1:1.5.
5. 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 1:0.03 to 1:1.5.
6. 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 1:0.2 to 1:7.
7. The thermoplastic resin composition according to 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 molding, a 35 μm thick copper layer is formed on the activated surface of the sample by electroplating, the sample is left in a chamber at 85 ℃ and 85% relative humidity for 120 hours, and after 100 grids each having a size of 1mm x 1mm are engraved on the copper layer, the thermoplastic resin composition has 92 to 100 grids which remain without being peeled off when an adhesive tape is attached to the injection molded sample and then peeled off from the injection molded sample.
8. The thermoplastic resin composition of claim 1, wherein said thermoplastic resin composition has a notched Izod impact strength of 15 kgf-cm/cm to 30 kgf-cm/cm when measured on a 1/8' thick sample according to ASTM D256.
9. The thermoplastic resin composition according to claim 1, wherein when at a molding temperature of 320 ℃, a mold temperature of 60 ℃,1,500 kgf/cm 2 Under the conditions of an injection pressure and an injection rate of 120mm/s, the thermoplastic resin composition has a helical flow length of 280mm to 350mm as measured after injection molding in a helical mold having dimensions of 15mm wide and 1mm thick.
10. A molded article produced from the thermoplastic resin composition according to any one of claims 1 to 9.
11. The molded article of claim 10, 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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| 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 |
|---|---|---|---|---|
| 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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| KR20210037906A (en) | 2021-04-07 |
| CN114450347A (en) | 2022-05-06 |
| WO2021066297A1 (en) | 2021-04-08 |
| KR102340429B1 (en) | 2021-12-16 |
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