KR100364627B1 - Polysulfone-based resin composition having excellent formability and electrostatic discharge property - Google Patents
Polysulfone-based resin composition having excellent formability and electrostatic discharge property Download PDFInfo
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- KR100364627B1 KR100364627B1 KR1019970072695A KR19970072695A KR100364627B1 KR 100364627 B1 KR100364627 B1 KR 100364627B1 KR 1019970072695 A KR1019970072695 A KR 1019970072695A KR 19970072695 A KR19970072695 A KR 19970072695A KR 100364627 B1 KR100364627 B1 KR 100364627B1
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- South Korea
- Prior art keywords
- weight
- parts
- resin composition
- polysulfone
- polycarbonate
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 37
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 25
- 239000004917 carbon fiber Substances 0.000 claims abstract description 25
- 229920000515 polycarbonate Polymers 0.000 claims abstract description 23
- 239000004417 polycarbonate Substances 0.000 claims abstract description 23
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims abstract description 18
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 10
- 239000003365 glass fiber Substances 0.000 claims abstract description 5
- 239000000454 talc Substances 0.000 claims abstract description 4
- 229910052623 talc Inorganic materials 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- -1 phenol compound Chemical class 0.000 claims description 6
- 150000002367 halogens Chemical group 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 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 10
- 239000002585 base Substances 0.000 description 9
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229920000412 polyarylene Polymers 0.000 description 7
- 125000005843 halogen group Chemical group 0.000 description 6
- 150000002989 phenols Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229930185605 Bisphenol Natural products 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920005668 polycarbonate resin Polymers 0.000 description 3
- 239000004431 polycarbonate resin Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003457 sulfones Chemical class 0.000 description 3
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 0 *C(*)(c(cc1)ccc1O)c(cc1)ccc1O Chemical compound *C(*)(c(cc1)ccc1O)c(cc1)ccc1O 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- ZAGYIPDRDJPYKU-UHFFFAOYSA-N 2,3-difluorocyclohexa-2,5-diene-1,4-dione Chemical compound FC1=C(F)C(=O)C=CC1=O ZAGYIPDRDJPYKU-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- YXVSYZRICGNXIH-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-2-phenylethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)CC1=CC=CC=C1 YXVSYZRICGNXIH-UHFFFAOYSA-N 0.000 description 1
- ODJUOZPKKHIEOZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3,5-dimethylphenyl)propan-2-yl]-2,6-dimethylphenol Chemical compound CC1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=C(C)C=2)=C1 ODJUOZPKKHIEOZ-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- 229920004011 Macrolon® Polymers 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920003289 Ultrason® S Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical group [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 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
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
-
- 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
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
발명의 분야Field of invention
본 발명은 성형성과 정전기 방전 특성이 우수한 폴리설폰계 수지 조성물에 관한 것이다. 보다 구체적으로 본 발명은 폴리설폰 및 폴리카보네이트/폴리알킬렌테레프탈레이트로 이루어진 기초수지, 탄소섬유 및 선택적으로 전도성 카본블랙 및/또는 충진제로 이루어진 성형성과 정전기 방전 특성이 우수한 수지 조성물에 관한 것이다.The present invention relates to a polysulfone resin composition having excellent moldability and electrostatic discharge characteristics. More specifically, the present invention relates to a resin composition having excellent moldability and electrostatic discharge characteristics composed of a base resin composed of polysulfone and polycarbonate / polyalkylene terephthalate, carbon fiber and optionally conductive carbon black and / or filler.
발명의 배경Background of the Invention
정밀전자 부품인 캐리어, 하우징 및 트레이 등에 적용이 되는 수지는 특히 대전방지성이나 전기전도 특성이 요구된다. 수지 조성물에 정전기 방전 특성이나 대전방지성을 부여하기 위하여 여러 방법이 제안되고 있다. 예를 들어 일본 특허공개 소61-243370호에서는 알킬렌 옥사이드가 10∼90 중량%인 폴리에테르아미드, 폴리에테르에스테르 또는 폴리에테르에스테르아미드를 적용하여 정전기 방전 특성이 오랫동안 지속되는 수지 조성물을 개시하고 있다. 그러나 이 방법으로 제조된 수지 조성물은 여러 수지와의 상용성이 충분하지 못하고 열안정성이 높지 못하며 그 자체의 고유저항 또는 표면저항이 만족할 만한 정도로 충분히 낮은 수준이 되지 못하여 사용범위가 좁은 단점이 있다.Resin applied to a precision electronic component carrier, housing and tray, etc., particularly requires antistatic properties and electrical conductivity characteristics. Various methods have been proposed in order to impart electrostatic discharge characteristics and antistatic properties to the resin composition. For example, Japanese Patent Application Laid-Open No. 61-243370 discloses a resin composition in which electrostatic discharge characteristics last for a long time by applying polyetheramide, polyetherester or polyetheresteramide having 10 to 90% by weight of alkylene oxide. . However, the resin composition prepared by this method has a disadvantage that the compatibility with various resins is not sufficient, the thermal stability is not high and its own resistivity or surface resistance is not sufficiently low to be satisfactorily low and the use range is narrow.
일본 특허공개 소53-61670호에서는 전도성 카본블랙을 첨가하여 표면저항 값이 1010Ω·sq 인 수지 조성물을 개시하고 있다. 그러나 첨가된 카본블랙의 양이 많아짐에 따라 점도가 점차 증가하여 가공특성이 저하되는 문제점이 있다. 또한 슬러핑(sloughing)을 유발하여 고도의 청정도를 요구하는 반도체 부품 가공중 클린룸이나 제품자체는 오염시키는 문제점도 발생된다.Japanese Patent Laid-Open No. 53-61670 discloses a resin composition having a surface resistance value of 10 10 Ω · sq by adding conductive carbon black. However, as the amount of added carbon black increases, there is a problem in that the viscosity is gradually increased and processing characteristics are lowered. In addition, there is a problem that the clean room or the product itself is contaminated during processing of semiconductor parts that require high cleanliness by causing sloughing.
미국 특허 제5,173,524호에서는 폴리설폰과 폴리페닐렌설파이드 혼합물에 카본블랙을 사용함으로써 내열성, 기계적 강도 및 전도성이 크게 향상된 수지 조성물이 개시되어 있다. 그러나 폴리페닐렌설파이드의 결정화로 인하여 성형시 수축되거나 크게 변형되는 등 치수안정성과 형태안정성이 저하되는 단점이 있다.U.S. Patent No. 5,173,524 discloses a resin composition in which heat resistance, mechanical strength and conductivity are greatly improved by using carbon black in a polysulfone and polyphenylene sulfide mixture. However, due to crystallization of polyphenylene sulfide, there is a disadvantage in that dimensional stability and shape stability are deteriorated, such as shrinkage or large deformation during molding.
일본 특허공개 소68-98632호에서는 폴리설폰계 수지 조성물에 유리섬유, 탄소섬유, 바륨설페이트 등을 첨가하여 형태안정성이 우수한 수지 조성물을 개시하고 있으나 전기전도 특성에 대해서는 언급된 바 없다.Japanese Patent Application Laid-Open No. 68-98632 discloses a resin composition having excellent shape stability by adding glass fiber, carbon fiber, barium sulfate, and the like to a polysulfone resin composition, but there is no mention of electrical conductivity properties.
유럽특허 제539936호에는 두 종류의 탄소 섬유를 ABS(아크릴로니트릴-부타디엔-스티렌) 수지에 10∼40 중량부의 양으로 투입하여 107Ω·cm 의 체적저항을 가지는 수지 조성물이 개시되어 있다. 또한 가장 최근에는 스테인레스틸 파이버 또는 금속 코팅된 탄소섬유를 적용하여 표면 저항을 10-1Ω·sq 이하로 낮추어 전자파차폐(EMI Shielding) 용도로 개발된 제품까지 출하되고 있다.EP 539936 discloses a resin composition having a volume resistivity of 10 7 Ω · cm by introducing two kinds of carbon fibers into an ABS (acrylonitrile-butadiene-styrene) resin in an amount of 10 to 40 parts by weight. Most recently, stainless steel fiber or metal-coated carbon fiber has been applied to lower the surface resistance to 10 -1 Ω · sq or less, and even products developed for EMI shielding are being shipped.
한편 최근의 연구결과에 따르면 동일한 양의 탄소섬유를 사용하더라도 전도성 카본블랙을 혼용하여 주면 탄소섬유만을 사용할 때보다는 전기전도도가 향상되는 것이 알려져 있다[Polymer Engineering and Science, Vol. 62, pp 2193∼2199(1996)].On the other hand, according to the recent research results, even if the same amount of carbon fiber is mixed with conductive carbon black is known to improve the electrical conductivity than using only carbon fiber [Polymer Engineering and Science, Vol. 62, pp 2193-2199 (1996).
상기에서 언급된 바와 같이 폴리설폰에 적용하여 탄소섬유를 적용하여 수지 조성물에 전도성을 부여하는 경우에 내열성, 강도, 전도도가 우수하게 되는 반면 폴리설폰 자체의 점도가 매우 높아 성형성이 낮은 문제점이 있다.As mentioned above, when the carbon fiber is applied to the polysulfone to impart conductivity to the resin composition, heat resistance, strength, and conductivity are excellent, whereas the polysulfone itself has a high viscosity and low moldability. .
이러한 문제점을 해결하는 방법으로 수지온도를 높이거나 사출압력/속도를 높이는 방법등이 있다. 그러나 이 방법들은 수지를 포함하는 조성물의 분해를 유발시킬 우려가 크고 최종제품내에 파이버의 방향으로 인해 높은 전류응력이 형성되어 실제 사용할 때 휨 현상이 발생하는 등 불량률을 증가시킬 가능성이 크다.As a solution to this problem, there is a method of increasing the resin temperature or increasing the injection pressure / speed. However, these methods have a high risk of causing decomposition of the composition containing the resin, and a high current stress is formed due to the direction of the fiber in the final product, which is likely to increase the defective rate such as warpage occurs in actual use.
따라서 본 발명자들은 폴리설폰에 폴리카보네이트와 폴리알킬렌테레프탈레이트를 첨가한 기초수지에 탄소섬유를 적용하고, 전도성 카본블랙 및/또는 충진제를 선택적으로 첨가하여 전도성, 내열성, 치수안정성, 성형성, 전전기 방전 특성 등이 우수한 수지 조성물을 개발하기에 이르렀다.Therefore, the present inventors apply carbon fiber to the base resin to which polycarbonate and polyalkylene terephthalate are added to polysulfone, and selectively add conductive carbon black and / or fillers to improve conductivity, heat resistance, dimensional stability, moldability, and electrical conductivity. The resin composition excellent in the electrical discharge characteristic etc. was developed.
발명의 목적Purpose of the Invention
본 발명의 목적은 폴리설폰에 폴리카보네이트/폴리알킬렌테레프탈레이트를 혼합시킨 수지 혼합물을 기초수지로 사용함으로써 치수안정성과 성형성이 우수한 수지 조성물을 제공하기 위한 것이다.An object of the present invention is to provide a resin composition excellent in dimensional stability and formability by using a resin mixture obtained by mixing polycarbonate / polyalkylene terephthalate with polysulfone as a base resin.
본 발명의 다른 목적은 폴리설폰계 수지에 탄소섬유를 첨가하여 정전기 방전특성이 우수한 수지 조성물을 제공하기 위한 것이다.Another object of the present invention is to provide a resin composition having excellent electrostatic discharge characteristics by adding carbon fiber to a polysulfone resin.
본 발명의 또 다른 목적은 폴리설폰계 수지에 전도성 카본블랙 및/또는 충진제를 첨가하여 기계적 물성이 우수한 수지 조성물을 제공하기 위한 것이다.Still another object of the present invention is to provide a resin composition having excellent mechanical properties by adding conductive carbon black and / or filler to polysulfone resin.
발명의 요약Summary of the Invention
본 발명의 수지 조성물은 폴리설폰 60∼80 중량%에 폴리카보네이트 10∼20 중량% 및 폴리알킬렌테레프탈레이트 10∼20 중량%를 혼합시킨 기초수지 100 중량부 및 탄소섬유 5∼20 중량부로 이루어진 정전기 방전 특성, 치수안정성, 성형성 등이 우수한 수지 조성물이다.The resin composition of the present invention is composed of 100 to 100 parts by weight of a base resin and 5 to 20 parts by weight of carbon fiber mixed with 60 to 80% by weight of polysulfone and 10 to 20% by weight of polycarbonate and 10 to 20% by weight of polyalkylene terephthalate. It is a resin composition which is excellent in discharge characteristics, dimensional stability, moldability, and the like.
본 발명의 목적에 따라 선택적으로 전도성 카본블랙 5∼10 중량부 및/또는 탈크, 유리섬유, 및 바륨설페이트중에서 선택된 하나 이상의 충진제 0∼20 중량부가 첨가될 수 있다.Optionally 5-10 parts by weight of conductive carbon black and / or 0-20 parts by weight of one or more fillers selected from talc, glass fibers, and barium sulphate may be added according to the purposes of the present invention.
발명의 구체예에 대한 상세한 설명Detailed Description of the Invention
본 발명의 수지 조성물은 폴리설폰에 폴리카보네이트와 폴리알킬렌테레프탈레이트를 혼합시킨 기초수지에 탄소섬유를 적용하고 선택적으로 전도성 카본 블랙과 충진제를 첨가하여 제조된다.The resin composition of the present invention is prepared by applying carbon fiber to a base resin in which polycarbonate and polyalkylene terephthalate are mixed with polysulfone, and optionally adding conductive carbon black and a filler.
하기에서 본 발명의 수지 조성물의 각 구성성분에 대하여 상세히 설명한다.Hereinafter, each component of the resin composition of this invention is demonstrated in detail.
본 발명에 사용되는 기초수지는 폴리설폰에 폴리카보네이트와 폴리알킬렌테레프탈레이트를 혼합시켜 사용한다.The base resin used in the present invention is used by mixing polycarbonate and polyalkylene terephthalate in polysulfone.
상기 폴리설폰 수지는 폴리아릴렌에테르의 일종이다. 폴리아릴렌에테르는 아릴렌 단위가 에테르(-O-), 케톤(-CO-) 또는 설폰(-SO2-)에 의하여 결합된 선형 열가소성 수지로서 방향족 폴리에테르를 의미한다.The polysulfone resin is a kind of polyarylene ether. Polyarylene ether means an aromatic polyether as a linear thermoplastic resin in which arylene units are bonded by ether (-O-), ketone (-CO-) or sulfone (-SO2-).
폴리아릴렌에테르는 디하이드릭 다핵 페놀과 디벤조노이드 화합물을 반응시켜 얻는다. 그 기본 구조는 O-E-O-E'으로 나타내어지며 E와 E'는 각각 디하이드릭 다핵 페놀과 디벤조노이드 화합물에서 기인하는 것으로서 ortho 또는 para 위치 둘 중의 하나에서 불활성의 전자를 끌어들이는 역할을 한다.Polyarylene ether is obtained by reacting a dihydric polynuclear phenol with a dibenzonoid compound. The basic structure is represented by O-E-O-E 'and E and E' are derived from dihydric multinuclear phenol and dibenzonoid compounds, respectively, and serve to attract inactive electrons in either ortho or para position.
폴리아릴렌에테르의 제조에 사용될 수 있는 디하이드릭 다핵 페놀에는 하기와 같은 구조식을 가지는 화합물이 있으며 이들을 불활성기로 치환시킨 유도체도 사용할 수 있고 두 종류 이상을 혼합하여 사용할 수 있다.Dihydric polynuclear phenols that can be used in the production of polyarylene ethers include compounds having the following structural formulas, and derivatives substituted with inert groups thereof may also be used, and two or more kinds thereof may be mixed.
상기식에서 R은 각각 수소, 저급 알킬, 알릴 또는 할로겐 치환기를 나타낸다.Wherein R represents hydrogen, lower alkyl, allyl or halogen substituents, respectively.
상기 구조식을 가지는 디하이드릭 다핵 페놀중 약산성의 디하이드릭 이핵 페놀이 바람직하며 디히드록시 디페닐 알칸 또는 이들의 핵을 할로겐으로 치환한 유도체가 더 바람직하게 사용될 수 있다. 그러한 예로는 2,2-비스(4-히드록시페닐)프로판, 1,1-비스(4-히드록시페닐)2-페닐에탄, 비스(4-히드록시페닐) 메탄 또는 이들의 벤젠고리의 수소중 하나 또는 두 개가 염소로 치환된 유도체가 있다. 이러한 대칭 또는 비대칭 연결 결합을 지니는 물질들을 비스페놀이라고 통칭한다. 이들을 연결시켜주는 결합에는 에테르, 카르보닐, 설폰 또는 이핵 페놀이 탄소에 연결된 탄화수소 잔기 등이 있다.Among the dihydric polynuclear phenols having the above structural formula, weakly acidic dihydric dinuclear phenols are preferable, and dihydroxy diphenyl alkanes or derivatives thereof substituted with halogens may be more preferably used. Examples include 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) 2-phenylethane, bis (4-hydroxyphenyl) methane or hydrogen in their benzene rings. And derivatives in which one or two of them are replaced with chlorine. Materials having such symmetrical or asymmetrical linkages are collectively called bisphenols. Bonds linking them include hydrocarbon residues in which ether, carbonyl, sulfone or dinuclear phenol is linked to carbon.
상기 디하이드릭 페놀과 반응되는 디벤조노이드 화합물로는 디할로벤조 노이드, 디니트로벤조노이드 또는 이들의 혼합물이 사용될 수 있다. 상기 벤조노이드 화합물은 벤젠고리의 ortho 또는 para 위치에 할로겐 원자나 나트로기와 같은 전자흡인기(electron withdrawing group)를 가지는 화합물이 바람직하다. 할로겐 원자나 니트로기가 동일한 벤젠고리에 결합된 1핵(mononuclear) 벤조노이드 화합물이나 서로 다른 벤젠고리에 결합된 다핵 벤조노이드 화합물이 모두 사용될 수 있으나 다핵 벤조노이드 화합물인 경우에는 활성 전자흡인기가 ortho나 para 위치에 있는 것이 바람직하다.As the dibenzonoid compound reacted with the dihydric phenol, dihalobenzonoid, dinitrobenzonoid or a mixture thereof may be used. The benzonoid compound is preferably a compound having an electron withdrawing group such as a halogen atom or a natro group at the ortho or para position of the benzene ring. A mononuclear benzonoid compound having a halogen atom or a nitro group bonded to the same benzene ring or a multinuclear benzonoid compound bonded to different benzene rings may be used. However, in the case of a multinuclear benzonoid compound, the active electron withdrawing group is ortho or para It is preferred to be in position.
디할로벤조노이드 화합물중 불소나 염소치환 벤조노이드 화합물이 주로 사용되며 불소치환 화합물은 반응속도가 빠르나 고가인 반면 염소치환 화합물은 상대적으로 저가이다. 중합반응계에 소량의 수분이 존재하는 경우에는 불소화합물이 바람직하게 사용될 수 있다. 그러나 이 경우에도 수분의 함량은 1%를 넘지 않아야 하며 0.5% 정도로 유지되는 것이 바람직하다.Fluorine or chlorine-substituted benzonoid compounds are mainly used among the dihalobenzonoid compounds. Fluorine-substituted compounds are fast and expensive, while chlorine-substituted compounds are relatively inexpensive. When a small amount of water is present in the polymerization reaction system, a fluorine compound can be preferably used. However, even in this case, the moisture content should not exceed 1% and preferably remain at about 0.5%.
전자흡인력을 가지는 활성기로 치환된 디할로벤조노이드 화합물도 사용될 수 있다. 이러한 활성기로는 단일 공유결합기로서 피리딘에서의 니트로 기 또는 할로겐기, 페닐설폰, 알킬설폰, 시아노, 트리플루오로메틸, 니트로소기 및 헤테로 질소원자 등과 같이 같은 고리상에 한 개 이상의 할로겐이나 니트로기를 활성화시킬 수 있는 것이 있으며, 이가 공유결합기로서 설폰기, 카르보닐기, 비닐리덴기, 설폭사이드기, 아조기, 포화 플루오로카본기, 포스핀 옥사이드기, 에틸리덴기과 같이 두 개의 다른 고리상의 할로겐이나 니트로기를 활성화시킬 수 있는 것이 있다. 이러한 화합물의 구체적인 예로는 강한 전자흡인력을 나타내는 설폰기를 가지는 4,4'-디클로로디페닐설폰 또는 4,4'-디플루오로디페닐설폰, 핵내 활성기를 가지는 디플루오로벤조퀴논, 1,4-, 1,5- 및 1,8-디플루오로안드라퀴논 등이 있다. 강한 전자흡인기를 가질수록 반응 속도가 빠르나 반응조건하에서 불활성을 유지하여야 한다.Dihalobenzonoid compounds substituted with an active group having an electron withdrawing force may also be used. Such activating groups include, as a single covalent group, one or more halogen or nitro groups on the same ring as the nitro group or halogen group in pyridine, phenylsulfone, alkylsulfone, cyano, trifluoromethyl, nitroso group and hetero nitrogen atom, etc. Some of them can be activated, and as divalent covalent groups, halogen or nitro groups on two different rings such as sulfone group, carbonyl group, vinylidene group, sulfoxide group, azo group, saturated fluorocarbon group, phosphine oxide group and ethylidene group can be activated. There is something that can be done. Specific examples of such a compound include 4,4'-dichlorodiphenylsulfone or 4,4'-difluorodiphenylsulfone having a sulfone group exhibiting strong electron attraction force, difluorobenzoquinone having 1,4-, 1,5- and 1,8-difluoroandhraquinones. The stronger the electron withdrawing group, the faster the reaction rate but the inertness should be maintained under the reaction conditions.
상기의 화합물외에도 할로겐이나 니트로기가 결합된 벤조노이드 핵에 수소원자나 전자공급기(electron supplying group)를 가진 것도 사용될 수 있다.In addition to the above compounds, those having a hydrogen atom or an electron supplying group in a benzonoid nucleus to which a halogen or a nitro group are bonded may be used.
두 종류 이상의 디할로벤조노이드 또는 디니트로벤조노이드 화합물을 혼합하여 사용할 수도 있다.Two or more types of dihalobenzonoid or dinitrobenzonoid compounds may be used in combination.
폴리아릴렌에테르는 디하이드릭 다핵 페놀과 디벤조노이드 화합물을 반응시켜 제조한다. 수분이 완전히 제거된 상태에서 고온의 액상 유기설폭사이드 또는 설폰 용제의 존재하에 디하이드릭 다핵 페놀의 제2가 알칼리 금속 염과 디벤조노이드 화합물을 동일 몰비로 1회 반응시켜 얻는다. 또한 디아히드릭 페놀을 금속염으로 전화시킨 다음 디벤조노이드 화합물과 반응시키는 2단계 공정으로도 제조될 수 있다. 즉 디하이드릭 다핵 페놀을 반응 용제내에서 알칼리 금속 안하이드리드, 알칼리 금속 히드록사이드 또는 알칼리 금속 알콕사이드 화합물과 in-situ 반응시켜 알칼리 금속으로 전환시킨 다음 생성된 물을 제거하여 무수 상태로 만든 후 디하이드릭 페놀의 디알칼리 금속염을 제조한다. 상기에서와 같은 조건하에서 디하이드릭 페놀의 디알칼리 금속염에 디벤조노이드 화합물을 화학적 당량으로 가하면서 반응시켜 얻는다. 고분자량을 확보하기 위해서는 반응기 내부는 확실히 무수 상태가 되어서 반응혼합물내의 수분함량이 0.5% 이하를 유지하는 것이 바람직하다. 생성된 폴리아릴렌에테르의 환원점도는 25℃, 메틸렌 클로라이드하에서 0.3∼1.5이다.Polyarylene ethers are prepared by reacting dihydric multinuclear phenols with dibenzonoid compounds. Obtained by reacting dihydric alkali metal salt of dihydric polynuclear phenol and dibenzonoid compound once in the same molar ratio in the presence of hot liquid organic sulfoxide or sulfone solvent in a state where water is completely removed. It can also be prepared in a two step process in which the dihydric phenol is converted to a metal salt and then reacted with a dibenzonoid compound. That is, the dihydric polynuclear phenol is reacted in-situ with an alkali metal anhydride, alkali metal hydroxide or alkali metal alkoxide compound in a reaction solvent to convert it into an alkali metal, and the resulting water is removed to make it anhydrous. A dialkali metal salt of dihydric phenol is prepared. It is obtained by reacting a dibenzonoid compound in chemical equivalents to the dialkali metal salt of dihydric phenol under the same conditions as described above. In order to secure a high molecular weight, it is preferable that the inside of the reactor is certainly anhydrous to maintain a water content of 0.5% or less in the reaction mixture. The reduced viscosity of the resulting polyarylene ether is 0.3-1.5 at 25 ° C. under methylene chloride.
디하이드릭 다핵 페놀과 디벤조노이드 화합물을 반응시켜 제조한 폴리아릴렌 에테르 수지중 하기 구조식 (I) 또는 (II)로 표현되는 폴리설폰 수지가 본 발명에 바람직하게 사용된다.Among the polyarylene ether resins prepared by reacting a dihydric polynuclear phenol with a dibenzonoid compound, a polysulfone resin represented by the following structural formula (I) or (II) is preferably used in the present invention.
상기 구조식(II)에서 R은 수소, 저급 알킬, 알릴 또는 할로겐 치환기를 나타낸다.In the above formula (II), R represents hydrogen, lower alkyl, allyl or halogen substituent.
본 발명에 사용되는 폴리설폰은 60∼80 중량%의 양으로 사용된다. 60 중량% 이상일 경우에는 폴리설폰이 매트릭스이거나 최소한 상호연속상(co-continuous phase)을 이룸으로써 만족할 만한 내열성 및 모듈러스를 얻을 수 있으나 60 중량% 미만인 경우에는 전체 수지 조성물의 매트릭스가 폴리설폰이 아닌 다른 수지 조성물이 되어 전체적으로 내열성이 저하되고 80 중량%를 초과하는 경우에는 수지 조성물의 점도가 지나치게 높아져서 가공 온도를 매우 높게 하여야 하므로 수지의 분해가능성이 커진다.Polysulfone used in the present invention is used in an amount of 60 to 80% by weight. If it is 60 wt% or more, the polysulfone is a matrix or at least a co-continuous phase to obtain satisfactory heat resistance and modulus, but if it is less than 60 wt%, the matrix of the entire resin composition is not polysulfone. When it becomes a resin composition and heat resistance falls overall and exceeds 80 weight%, since the viscosity of a resin composition becomes high too much and processing temperature must be made very high, the disassembly possibility of resin becomes large.
본 발명에서는 상기 폴리설폰에 폴리카보네이트와 폴리알킬렌테레프탈레이트를 혼합하여 사용한다. 상기 폴리카보네이트와 폴리알킬렌테레프탈레이트의 제조방법과 열가소성 수지 조성물에의 응용은 이 분야에서 잘 알려져있다.In the present invention, the polysulfone is used by mixing a polycarbonate and a polyalkylene terephthalate. Methods of preparing the polycarbonates and polyalkylene terephthalates and their application to thermoplastic resin compositions are well known in the art.
폴리카보네이트 수지는 분자량 조절제와 촉매의 존재하에서 디하이드릭 페놀과 포스겐을 반응시켜 제조하거나 디하이드릭 페놀과 디페닐카보네이트와 같은 카보네이트 전구체의 에스테르 상호교환 반응을 이용하여 제조할 수 있다.The polycarbonate resin may be prepared by reacting dihydric phenol with phosgene in the presence of a molecular weight modifier and a catalyst or by using an ester interchange reaction of a carbonate precursor such as dihydric phenol and diphenylcarbonate.
바람직하게 사용될 수 있는 디하이드릭 페놀은 비스페놀이며 이중 비스 페놀 A인 2,2-비스(4-히드록시페닐)프로판이 가장 바람직하다. 바람직하게 사용될 수 있는 다른 디하이드릭 페놀에는 히드로퀴논, 4-4'-디히드록시디페닐, 비스(4-히드록시페닐)메탄, 1,1-비스(4-히드록시페닐)시클로헥산, 2,2-비스(3,5-디메틸-4-히드록시페닐)프로판, 비스(4-히드록시페닐)설파이드, 비스(4-히드록시페닐)설폰, 비스(4-히드록시페닐)설폭사이드, 비스(4-히드록시페닐)케톤, 비스(4-히드록시페닐)에테르 및 2,2-비스(3,5-디브로모-4-히드록시페닐)프로판 같은 할로겐화 비스페놀등이 있다.The dihydric phenol that can be preferably used is bisphenol, of which bisphenol A, 2,2-bis (4-hydroxyphenyl) propane, is most preferred. Other dihydric phenols that may be preferably used include hydroquinone, 4-4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2 , 2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, Halogenated bisphenols such as bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether and 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.
폴리카보네이트 수지는 단일중합체, 두 종류 이상의 디하이드릭 페놀의 공중합체 또는 이들의 혼합물일 수 있다. 여기에는 선형 폴리카보네이트, 분지된 폴리카보네이트 및 폴리에스테르카보네이트가 있다. 선형 폴리카보네이트는 비스페놀 A계 폴리카보네이트가 바람직하고 분지된 폴리카보네이트로는 트리멜리틱 무수물, 트리멜리틱산과 같은 다관능성 방향족 화합물을 디하이드릭 페놀과 카보네이트 전구체와 반응시켜 제조된 수지가 바람직하며 폴리에스테르카보네이트는 이관능성 카르복실산을 디하이드릭 페놀과 카보네이트 전구체와 반응시켜 제조된 수지가 바람직하다.The polycarbonate resin may be a homopolymer, a copolymer of two or more dihydric phenols, or a mixture thereof. These include linear polycarbonates, branched polycarbonates and polyestercarbonates. The linear polycarbonate is preferably a bisphenol A-based polycarbonate, and the branched polycarbonate is preferably a resin prepared by reacting a polyfunctional aromatic compound such as trimellitic anhydride and trimellitic acid with a dihydric phenol and a carbonate precursor. The ester carbonate is preferably a resin prepared by reacting a bifunctional carboxylic acid with a dihydric phenol and a carbonate precursor.
본 발명에 바람직하게 사용될 수 있는 폴리카보네이트는 비스페놀 폴리 카보네이트 수지이며, 분자량은 특별히 제한되지는 않으나, 수지 조성물의 기계적 특성이나 작업성 등을 고려하면 중량평균 분자량이 20,000 내지 80,000인 것이 바람직하며 18,000∼27,000인 것이 더욱 바람직하다.Polycarbonate that can be preferably used in the present invention is a bisphenol polycarbonate resin, the molecular weight is not particularly limited, but considering the mechanical properties and workability of the resin composition, the weight average molecular weight is preferably 20,000 to 80,000, and 18,000 to It is more preferable that it is 27,000.
폴리알킬렌테레프탈레이트는 여러 회사에서 다양한 상품명으로 시판되고 있으며 테레프탈산 또는 디메틸테레프탈레이트와 테트라메틸렌글리콜을 이용하여 제조할 수 있다. 폴리알킬렌테레프탈레이트의 분자량은 특별히 제한되지는 않으나 수지 조성물의 기계적 특성이 내열성 등을 고려한다면 수평균분자량이 10,000 내지 100,000인 것이 바람직하다.Polyalkylene terephthalates are commercially available from various companies under various trade names and can be prepared using terephthalic acid or dimethyl terephthalate and tetramethylene glycol. The molecular weight of the polyalkylene terephthalate is not particularly limited, but the number average molecular weight is preferably 10,000 to 100,000 if the mechanical properties of the resin composition consider heat resistance and the like.
상기 폴리카보네이트와 폴리알킬렌테레프탈레이트는 2 : 1∼1 : 2의 비율로 혼합하여 사용한다. 혼합비율이 2 : 1 미만인 경우 전체 조성물의 점도를 낮추어 성형성을 향상시키는 효과가 미약하고 1 : 2 이상인 경우에는 폴리알킬렌테레프탈레이트가 전체 블렌드의 매트릭스 형성에 참여하게 되어 내열성을 급격히 저하시킬 우려가 크고 또 결정화도가 일어나 후수축등으로 최종제품에 휨등의 불량이 발생할 우려가 높다.The polycarbonate and the polyalkylene terephthalate are used by mixing in a ratio of 2: 1 to 1: 2. If the mixing ratio is less than 2: 1, the effect of lowering the viscosity of the entire composition to improve moldability is insignificant, and if the ratio is 1: 2 or more, polyalkylene terephthalate may participate in matrix formation of the entire blend, which may drastically lower heat resistance. The crystallinity is high, and there is a high possibility that defects such as warpage may occur in the final product due to post-shrinkage.
상기 폴리카보네이트와 폴리알킬렌테레프탈레이트는 20∼40 중량%의 양으로 사용된다.The polycarbonate and polyalkylene terephthalate are used in an amount of 20 to 40% by weight.
상기 기초수지가 첨가되어 사용되는 탄소섬유는 길이가 3∼10mm이고 직경이 7㎛인 PAN(폴리아크릴로니트릴)계 필라멘트이다. 최종 제품에서 적절한 수준의 전기전도성을 유지하기 위해서는, 탄소섬유가 압출기 안에서 수지와 혼련될 때 스크류에 의해 절단되는 것을 감안하면 그 길이가 최소 3mm 이상이어야 하며 10mm를 초과하게 되면 압출시에 스크류에 지나친 토크를 발생시키고 충분한 분산이 어려워 성형품의 외관 역시 나빠진다.The carbon fiber used by adding the base resin is a PAN (polyacrylonitrile) filament having a length of 3 to 10 mm and a diameter of 7 μm. In order to maintain an appropriate level of electrical conductivity in the final product, the length of the carbon fiber should be at least 3 mm, if it is cut by the screw when kneaded with the resin in the extruder. The appearance of the molded part is also deteriorated due to the occurrence of torque and difficulty in dispersion.
탄소섬유의 사용량은 기초수지 100 중량부에 대하여 5∼20 중량부가 적합한데 5 중량부 이하로 사용한 경우에는 전기전도도 부여 정도가 낮아서 발생되는 정전기의 방전하는 능력이 떨어져 오염 물질이 부착되어 제품을 오염시키거나, 정전기 발생이 매우 높을 경우에는 전기 스파크로 인해 보호해야 할 반도체내의 회로가 손상되는등 치명적인 손실을 입힐 수 있다. 또 20 중량부 이상으로 사용할 경우에는 더 이상의 전기전도도 증가를 기대하기 어렵고 기계적 강성증가에 비하여 점도가 크게 증가하여 성형성을 저하시킬 우려가 있다. 특히 탄소섬유의 가격이 수지에 비하여 매우 고가인 점을 감안할 때 표면저항이 103Ω·sq 이하인 전도도를 부여하기 위해서는 탄소섬유보다는 오히려 스텐레스 스틸 파이버나 금속코팅 탄소섬유를 사용하는 것이 더욱 바람직하다.The amount of carbon fiber used is 5 to 20 parts by weight based on 100 parts by weight of the basic resin, but when it is used at 5 parts by weight or less, the conductivity of electrostatic discharge is low due to the low degree of electrical conductivity. In the event of a very high static charge, electrical sparks can cause catastrophic losses, such as damage to circuits in the semiconductor to be protected. In addition, when used in an amount of 20 parts by weight or more, it is difficult to expect an increase in the electrical conductivity any more, and there is a fear that the viscosity increases significantly compared to the increase in mechanical rigidity, thereby degrading the formability. In particular, considering that carbon fibers are very expensive compared to resins, it is more preferable to use stainless steel fibers or metal-coated carbon fibers rather than carbon fibers in order to impart conductivity having a surface resistance of 10 3 Ω · sq or less.
본 발명의 수지 조성물의 전기전도도를 향상시키기 위하여 전도성 카본 블랙을 첨가한다. 카본블랙은 수분률이 1.0 % 미만, 비표면적이 1,000∼1,500 ㎡/g이고 내부 포어(pore) 체적은 480∼510 mL/100g 이고 평균입자크기는 250∼350Å인 것이 바람직하게 사용될 수 있다.Conductive carbon black is added to improve the electrical conductivity of the resin composition of the present invention. Carbon black may preferably be used having a moisture content of less than 1.0%, a specific surface area of 1,000 to 1500 m 2 / g, an internal pore volume of 480 to 510 mL / 100 g, and an average particle size of 250 to 350 mm 3.
사용되는 전도성 카본블랙의 함량은 기초수지 100 중량부에 대하여 5∼10 중량부이고 3∼6 중량부의 양으로 사용되는 것이 바람직하다. 3 중량부 이하인 경우에는 탄소섬유와 혼용되어도 전기전도도를 향상시키는 효과를 기대하기 어렵고, 6 중량부 이상인 경우에는 슬러핑 문제가 대두될 우려가 커지기 때문이다.The content of the conductive carbon black used is 5 to 10 parts by weight and 3 to 6 parts by weight based on 100 parts by weight of the base resin. If it is 3 parts by weight or less, even when mixed with carbon fiber, it is difficult to expect the effect of improving the electrical conductivity, and when it is 6 parts by weight or more, there is an increased risk of sluffing problems.
이외에 탈크, 글라스파이버, 바륨설페이트 등의 충진제가 필요에 따라 적정량 사용되어 휨 및 수축을 억제하는데 보조적으로 사용될 수 있다.In addition, fillers such as talc, glass fiber, and barium sulfate may be used in an appropriate amount as necessary to assist in suppressing warpage and shrinkage.
본 발명의 수지 조성물은 폴리설폰, 폴리카보네이트 및 폴리알킬렌테레프탈레이트를 혼합한 기초수지에 선택적으로 전도성 카본블랙 및/또는 충진제를 첨가하여 헨셀믹서, 텀블러 또는 나우다 믹서 등을 사전에 드라이 블렌딩한다. 이 혼합물을 270∼290℃에서 이축스크류 압출기를 통하여 압출한다. 이때 탄소섬유를 이축압출기의 적절한 위치에서 사이드 피더를 통하여 투입시킨다. 이것은 압출기의 과도한 부하를 막고 탄소섬유의 지나친 절단을 예방하기 위함이다. 이축압출기를 이용하여 만들어진 스트랜드 형태의 펠렛 모양으로 자른 다음 120℃에서 3시간 이상 건조한 후 금형에 사출성형하여 성형품을 제조한다.The resin composition of the present invention dry blends a Henschel mixer, tumbler, or Nada mixer in advance by selectively adding conductive carbon black and / or filler to a base resin mixed with polysulfone, polycarbonate and polyalkylene terephthalate. . The mixture is extruded through a twin screw extruder at 270 to 290 ° C. At this time, the carbon fiber is introduced through the side feeder at an appropriate position of the twin screw extruder. This is to prevent excessive load of the extruder and to prevent excessive cutting of the carbon fiber. Cut into strand-shaped pellets made using a twin screw extruder, and then dried at 120 ° C. for at least 3 hours to manufacture a molded article by injection molding into a mold.
본 발명은 하기의 실시예에 의해서 구체화될 것이며 하기의 실시예는 본 발명의 구체적 예시에 불과하며 본 발명의 보호범위를 한정하거나 제한하는 것은 아니다.The present invention will be embodied by the following examples, which are only illustrative of the present invention and do not limit or limit the scope of the present invention.
실시예Example
본 발명의 실시예에 사용된 성분의 제조 및 사양은 다음과 같다.Preparation and specification of the components used in the examples of the present invention are as follows.
폴리설폰: 시차주사 열분석기를 이용한 유리전이온도가 194℃이고 중량평균분자량이 24,000인 BASF사의 울트라슨에스 2010을 사용하였다.Polysulfone: A BASF Ultrason S 2010 with a glass transition temperature of 194 ° C. and a weight average molecular weight of 24,000 was used.
폴리카보네이트: 유리전이온도가 153℃이고 중량 평균 분자량이 27000인 비스페놀 A 폴리카보네이트(Bayer사의 마크롤론 2800)를 사용하였다.Polycarbonate: Bisphenol A polycarbonate (Macrolon 2800 from Bayer) having a glass transition temperature of 153 ° C. and a weight average molecular weight of 27000 was used.
폴리알킬렌테레프탈레이트: 유리전이온도가 70℃이고 용융온도가 230℃인 폴리(1,4-부틸렌테레프탈레이트) ((주)선경인더스트리(SKI)의 SKYTON1100D)를 사용하였다.Polyalkylene terephthalate: Poly (1,4-butylene terephthalate) (SKYTON1100D of SunKK Industries, Inc.) having a glass transition temperature of 70 ° C. and a melting temperature of 230 ° C. was used.
탄소섬유: Toray사의 토레이카 XG-06을 사용하였다.Carbon fiber: Toray Toraya XG-06 was used.
카본블랙: Lion Chemical사의 캐첸블랙 EC 600을 GE 플라스틱의 폴리카보네이트 LEXAN 121에 25 중량% 투입하여 만든 마스터뱃치를 사용하였다.Carbon black: A masterbatch made by adding 25 wt% of Catenblack EC 600 from Lion Chemical to polycarbonate LEXAN 121 of GE plastic was used.
본 발명의 수지 조성물의 성분을 표 1의 조성비대로 헨셀믹서를 이용하여 드라이 블렌딩한 후 이 혼합물을 바렐온도 270∼290℃, 직경 30mm, L/D=30의 이축 스크류 압출기를 이용하여 압출하였다. 이때 탄소섬유는 사이드 피더를 통하여 별도로 투입하였다. 이축압출기로 압출된 스트랜드 모양의 혼합물을 펠렛 모양으로 자른 후 120℃에서 3시간 이상 건조시킨 다음 물성 시험용 금형에 사출성형하여 시편(128×12.8×6.4㎣)을 제조하였다. 사출시 실린더온도는 270℃로 조절하였다.The components of the resin composition of the present invention were dry blended using a Henschel mixer according to the composition ratios in Table 1, and the mixture was extruded using a twin screw extruder having a barrel temperature of 270 to 290 ° C, a diameter of 30 mm, and an L / D = 30. At this time, the carbon fiber was added separately through the side feeder. The strand-shaped mixture extruded by a twin screw extruder was cut into pellets, dried at 120 ° C. for at least 3 hours, and then injection molded into a test mold for physical properties to prepare a specimen (128 × 12.8 × 6.4 mm 3). The cylinder temperature during injection was adjusted to 270 ° C.
비교실시예Comparative Example
수지성분의 조성비는 표 1에 나타나 있으며 나머지는 모두 실시예와 동일한방법으로 시편을 제조하였다.The composition ratio of the resin component is shown in Table 1, and the rest were all prepared in the same manner as in Example.
표 1Table 1
표
성형된 시편에 대하여 굴곡강도, 굴곡탄성률, 유동지수 및 표면저항을 표준방법으로 측정하였고 그 결과를 표 2에 기재하였다.Flexural strength, flexural modulus, flow index and surface resistance of the molded specimens were measured by standard methods and the results are shown in Table 2.
표 2TABLE 2
Claims (4)
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| KR1019970072695A KR100364627B1 (en) | 1997-12-23 | 1997-12-23 | Polysulfone-based resin composition having excellent formability and electrostatic discharge property |
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