US20130237644A1 - Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate - Google Patents
Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate Download PDFInfo
- Publication number
- US20130237644A1 US20130237644A1 US13/743,934 US201313743934A US2013237644A1 US 20130237644 A1 US20130237644 A1 US 20130237644A1 US 201313743934 A US201313743934 A US 201313743934A US 2013237644 A1 US2013237644 A1 US 2013237644A1
- Authority
- US
- United States
- Prior art keywords
- copier
- exterior part
- acrylonitrile
- toughener
- glycidyl methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 229920000139 polyethylene terephthalate Polymers 0.000 title claims abstract description 77
- 239000005020 polyethylene terephthalate Substances 0.000 title claims abstract description 77
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 62
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 62
- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 28
- 229920001897 terpolymer Polymers 0.000 claims abstract description 54
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000012745 toughening agent Substances 0.000 claims abstract description 41
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 40
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims description 68
- 239000000463 material Substances 0.000 claims description 37
- 239000011258 core-shell material Substances 0.000 claims description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 14
- 229920002379 silicone rubber Polymers 0.000 claims description 13
- 239000004945 silicone rubber Substances 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- UHFOGRFLWQICFT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)-1,1-diphenylpropane-1,3-diol phosphono dihydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)O.C1(=CC=CC=C1)C(O)(C(CO)(CO)CO)C1=CC=CC=C1 UHFOGRFLWQICFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical group C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006757 chemical reactions by type Methods 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 150000004712 monophosphates Chemical class 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- 229920002842 oligophosphate Polymers 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical group COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Polymers OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 4
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical group C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 3
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical group CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- BQPNUOYXSVUVMY-UHFFFAOYSA-N [4-[2-(4-diphenoxyphosphoryloxyphenyl)propan-2-yl]phenyl] diphenyl phosphate Chemical compound C=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 BQPNUOYXSVUVMY-UHFFFAOYSA-N 0.000 claims description 2
- QYMGIIIPAFAFRX-UHFFFAOYSA-N butyl prop-2-enoate;ethene Chemical compound C=C.CCCCOC(=O)C=C QYMGIIIPAFAFRX-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- XTBBZRRBOAVBRA-UHFFFAOYSA-N dimethyl phenyl phosphate Chemical compound COP(=O)(OC)OC1=CC=CC=C1 XTBBZRRBOAVBRA-UHFFFAOYSA-N 0.000 claims description 2
- 229920006245 ethylene-butyl acrylate Polymers 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 67
- 238000000034 method Methods 0.000 description 49
- 238000003672 processing method Methods 0.000 description 13
- 239000008188 pellet Substances 0.000 description 12
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 239000002699 waste material Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000013502 plastic waste Substances 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OXOPJJPCBRTSLW-PGUFJCEWSA-N (2R)-2-(3,5-ditert-butyl-4-hydroxyphenyl)-2-methylicosanoic acid Chemical compound CCCCCCCCCCCCCCCCCC[C@](C)(C1=CC(=C(C(=C1)C(C)(C)C)O)C(C)(C)C)C(=O)O OXOPJJPCBRTSLW-PGUFJCEWSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229920006164 aromatic vinyl copolymer Polymers 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding 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
- 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
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
-
- 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
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the present invention relates to a composition and use of the composition, and, in particular, relates to a halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate and a copier/printer exterior part using the resin composition.
- plastic waste has increased, and a huge amount of energy sources has been wasted. Accordingly, collection and reuse of plastic waste has attracted more attention than before.
- Plastic materials are chemicals derived from petroleum. It is well known that petroleum is a lifeline for the industries of the present age and a natural source which cannot be reproduced. According to statics of a related organization, plastic waste generated by one medium-sized city per year can cover plastic materials demanded by 20 small and medium-sized plastics companies per year. Hence, reuse of plastics can be regarded as reuse of petroleum. By melting and granulating plastic waste, supply-demand imbalance in plastic materials can be reduced, and a national budget for petroleum import can be drastically cut.
- PC Polycarbonate
- PC has excellent impact resistance, heat resistance, dimensional stability, electric insulation and the like, is nontoxic, and has low water absorbency. Accordingly, PC can be used in a wide range of temperatures.
- PC has high light transmittance of 90%, it is named “transparent metal”, and used instead of copper or other colored metals in various fields, such as the electrical and electronic industry, the automobile industry, the mechanical industry, the optical industry, and the pharmaceutical industry.
- consumption of PC has rapidly and continuously increased, and unavoidably, a large amount of PC waste has been generated.
- PC waste is an important recycled source, and it is necessary to properly process PC waste so as to reduce influence of PC waste on environments. Collection and reuse of PC waste contribute to economic and social benefits significantly. Examples of PC waste to be collected include PC used in buckets, dies, and optical disks.
- PET polyethylene terephthalate
- production capacity of polyethylene terephthalate (PET) in the world reached 67 million tons, and output thereof was 61 million tons.
- PET waste which is generated by consumption of a large amount of PET, is generated every year. If PET waste is not sufficiently used, a large amount of resources is wasted.
- recycled PET is mainly used in fibers, sheets, and bottles for containing nonfood, and used in some plastic bottles, monofilaments, and the like.
- the application range of recycled PET is relatively narrow in the engineering plastic field. In particular, application thereof in the plastic alloy field is hardly reported.
- Engineering PET has low viscosity/toughness in general, and recycled PET has lower viscosity/toughness. Hence, unless the viscosity/toughness is increased, the application range of recycled PET is not widened. Furthermore, influence of low molecular weights and wide distribution of molecular weights of recycled PET on performance thereof is more than that of recycled PC on performance thereof, and hence a composition including recycled PET and a product using the composition are unstable in performance, and difficult to obtain stable mechanical performance. Consequently, the application range of recycled PET is somewhat limited.
- halogen-free flame-retardant resin composition including recycled PET and recycled PC and a product using the resin composition has an important meaning in terms of environmental protection and practical application.
- the present invention is made in view of the circumstances, and objects of the present invention include providing a halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate and a copier/printer exterior part using the resin composition, each of which can realize cycle use (recycling) of polycarbonate and polyethylene terephthalate, and prevent stability of mechanical performance of materials (components) of the resin composition from decreasing.
- a copier/printer exterior part using a halogen-free flame-retardant resin composition including: 5 wt % to 50 wt % of unused polycarbonate; 20 wt % to 63 wt % of recycled polycarbonate; 5 wt % to 35 wt % of recycled polyethylene terephthalate; 0.2 wt % to 2 wt % of a styrene-acrylonitrile-glycidyl methacrylate terpolymer; 5 wt % to 15 wt % of a toughener; 10 wt % to 20 wt % of a flame retardant; 0.1 wt % to 0.8 wt % of a flame-retardant antidrip agent; 0.1 wt % to 1 wt % of an antioxidant; and 0.1 wt % to 2
- FIG. 1 shows external appearance of a copier using an exterior part in accordance with an example of the present invention
- FIG. 2 is a perspective view of the exterior part (outside dimensions: length of 500 mm, width of 600 mm, and thickness of 2.5 mm) using a resin composition in accordance with an example of the present invention.
- An exterior part for a copier or a printer (a copier/printer exterior part 1 shown in FIG. 2 ) of the present invention is used in a scanner which reads an original document, a copier which prints the original document read by the scanner, a printer or a facsimile apparatus which prints image data inputted from an external apparatus, or a multifunctional machine called MFP (Multi Function Peripheral) which has these functions.
- the copier/printer exterior part 1 of the present invention is used for exterior parts G 1 to G 9 of a copier shown in FIG. 1 , for example.
- the copier/printer exterior part 1 is provided with pin side gates 2 as shown in FIG. 2 .
- an “unused” component indicates that the component has not been used yet
- a “recycled” component indicates that the component has been used before. That is, for example, “unused polycarbonate (PC)” indicates that the PC has not been used, and “recycled polycarbonate (PC)” indicates that the PC has been used before.
- Component A-1 unused PC having a weight average molecular weight of 25000, produced by HONAM Petrochemical Corp.
- Component A-2 unused PC having a weight average molecular weight of 21000, produced by HONAM Petrochemical Corp.
- Component A-3 recycled PC having a weight average molecular weight of 24000, on the market
- Component B-1 recycled PET derived from PET bottles/sheets for drinks, and having a viscosity of 0.8 dl/g, on the market
- Component B-2 unused PET having a viscosity of 1.0 dl/g, produced by Jinshan Petrochemical Company
- Component C-1 styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 8 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-2 styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 5 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-3 styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-3a styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 35 wt % acrylonitrile
- Component C-3b styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 30 wt % acrylonitrile
- Component C-3c styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 27 wt % acrylonitrile
- Component C-3d styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 20 wt % acrylonitrile
- Component C-3e styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 15 wt % acrylonitrile
- Component C-4 styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 1 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-5 styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 0.5 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component D-1 MBS EM-500, produced by LG Electronics
- Component D-2 acrylic acid-silicone rubber system toughener, S-2001, produced by Mitsubishi Rayon Co., Ltd.
- Component D-3 acrylonitrile-butadiene-styrene copolymer toughener containing 54 wt % butadiene, 34 wt % styrene and 12 wt % acrylonitrile, produced by Korea Kumho Petrochemical Co., Ltd.
- Component E flame retardant, BDP, produced by Great Lakes Chemical Corporation
- Component F flame-retardant antidrip agent, AS-coated polytetrafluoroethylene system flame-retardant antidrip agent containing 50 wt % polytetrafluoroethylene, on the market
- Component G processing aid containing, for example, ethylenebisstearamide (lubricant), IRGAFOS®168 (phosphite (phosphoric acid ester) system antioxidant), IRGANOX®1076 (hindered phenol system antioxidant), and DOW CORNING® MB-50 (lubricant), and having a weight ratio of ethylenebisstearamide, IRGAFOS®168, IRGANOX®1076 and DOW CORNING® MB-50 being 2:2:1:1
- MI Melt Index
- Each of Examples 1 to 10 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- the preparation method of the halogen-free flame-retardant resin composition of each of Examples 1 to 10 included the following steps of:
- Each of Comparative Examples 1, 2, 8 and 9 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- the preparation method of the halogen-free flame-retardant resin composition of each of Comparative Examples 1, 2, 8 and 9 included the following steps of:
- Each of Comparative Examples 3 to 7 and 10 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- the preparation method of the halogen-free flame-retardant resin composition of each of Comparative Examples 3 to 7 and 10 included the following steps of
- Each of Comparative Examples 11 to 16 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- the preparation method of the halogen-free flame-retardant resin composition of each of Comparative Examples 11 to 16 included the following steps of
- the Styrene-Acrylonitrile-Glycidyl Methacrylate Terpolymer Contain 1 wt % to 5 wt % Glycidyl Methacrylate and 27 wt % to 30 wt % Acrylonitrile.
- impact strength the notched Izod impact strength (“impact strength” hereinafter) of Comparative Examples 3 and 4 was significantly lower than that of Example 1.
- the difference between Example 1 and Comparative Examples 3 and 4 was the component C. That is, Example 1, Comparative Example 3 and Comparative Example 4 used the components C-3, C-1 and C-5, respectively.
- Each of the components C-3, C-1 and C-5 was a styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 28 wt % acrylonitrile.
- the components C-3 (Example 1), C-1 (Comparative Example 3) and C-5 (Comparative Example 4) contained 2 wt %, 8 wt % and 0.5 wt % glycidyl methacrylate, respectively.
- the halogen-free flame-retardant resin composition which contains the styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate is excellent in mechanical performance.
- Example 1 When Example 1 was compared with Examples 5 and 6, as shown in TABLE 1, the impact strength of Examples 1, 5 and 6 was high. Examples 1, 5 and 6 used the components C-3, C-2 and C-4, respectively. Each of the components C-3, C-2 and C-4 was a styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 28 wt % acrylonitrile.
- Example 1 was compared with Comparative Examples 11, 12, 13, 14 and 15, as shown in TABLE 1 and TABLE 3, the impact strength of Example 1 was high, and the impact strength of Comparative Examples 12 and 13 was relatively high too.
- Example 1 The difference between Example 1 and Comparative Examples 11, 12, 13, 14 and 15 was the content (wt %) of acrylonitrile in the styrene-acrylonitrile-glycidyl methacrylate terpolymer (component C-3, C-3a, C-3b, C-3c, C-3d or C-3e).
- the contents of acrylonitrile of the components C-3 (Example 1), C-3a (Comparative Example 11), C-3b (Comparative Example 12), C-3c (Comparative Example 13), C-3d (Comparative Example 14) and C-3e (Comparative Example 15) were 28 wt %, 35 wt %, 30 wt %, 27 wt %, 20 wt % and 15 wt %, respectively. Therefore, it is preferable that the component, namely, the styrene-acrylonitrile-glycidyl methacrylate terpolymer, contain 27 wt % to 30 wt % acrylonitrile.
- the terpolymer when a styrene-acrylonitrile-glycidyl methacrylate terpolymer is used in the halogen-free flame-retardant resin composition, it is preferable that the terpolymer contain 1 wt % to 5 wt % glycidyl methacrylate and 27 wt % to 30 wt % acrylonitrile.
- Halogen-Free Flame-Retardant Resin Composition Contain 0.2 wt % to 2 wt % Styrene-Acrylonitrile-Glycidyl Methacrylate Terpolymer.
- Examples 1, 7 and 8 The difference between Examples 1, 7 and 8 was the content of the component C-3.
- the contents of the component C-3 of Examples 1, 7 and 8 were 0.4 wt %, 0.2 wt % and 2 wt %, respectively.
- the halogen-free flame-retardant resin composition contain 0.2 wt % to 2 wt % styrene-acrylonitrile-glycidyl methacrylate terpolymer.
- Halogen-Free Flame-Retardant Resin Composition is Prepared by Using the Two-Step Method as the Processing Method.
- Halogen-Free Flame-Retardant Resin Composition Contains Less than 30 wt % Recycled PET.
- Example 10 when Example 10 was compared with Comparative Example 10, as shown in TABLE 1 and TABLE 2, the impact strength of Comparative Example 10 was significantly lower than that of Example 10.
- the difference between Example and Comparative Example 10 was the content of recycled PET. This indicates that, if the halogen-free flame-retardant resin composition contains more than 30 wt % recycled PET, the impact strength significantly decreases, and may exert a bad influence on the composition in terms of practical application.
- the halogen-free flame-retardant resin composition contain less than 30 wt % recycled PET.
- Example 1 was compared with Comparative Example 16, as shown in TABLE 1 and TABLE 3, “Example 1>Comparative Example 16” was true in impact strength.
- the difference between Example 1 and Comparative Example 16 was PET.
- Example 1 used recycled PET, and the recycled PET had been processed by the component C-3, while Comparative Example 16 used unused PET having a high viscosity.
- Example 1 When Example 1 was compared with Example 4, as shown in TABLE 1, the impact strength of Example 1 was almost the same as that of Example 4. This indicates that the influence of the content of recycled PC on the impact strength can be controlled.
- Examples 1, 2 and 3 were compared with each other, as shown in TABLE 1, the impact strength thereof was almost the same.
- the difference between Examples 1, 2 and 3 was the toughener.
- Examples 1, 2 and 3 used, as the toughener, the components D1, D2 and D3, which is a mixture of the components D1 and D2, respectively. This indicates that both the core-shell structured acrylate system toughener and the core-shell structured acrylate-silicone rubber system toughener are relatively effective in toughening the composition.
- Component A-1a Unused PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000
- Component A-2a Unused PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 40000
- Component A-3a Recycled PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000
- Component A-3b Recycled PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 40000
- Component B-1a Recycled PET having a viscosity of 0.65 dl/g, on the market
- Component B-1b Recycled PET having a viscosity of 0.90 dl/g, on the market
- Component C-6 styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 33 wt % acrylonitrile, produced in-house
- Component C-7 styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 3 wt % glycidyl methacrylate and 20 wt % acrylonitrile, produced in-house
- Component D-4 ethylene-methyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate copolymer having a weight ratio of ethylene-methyl acrylate copolymer to ethylene-methyl acrylate-glycidyl methacrylate copolymer being 1:1
- Component D-5 methyl methacrylate-silicone rubber copolymer and acrylonitrile-butadiene-acrylic ester copolymer having a weight ratio of methyl methacrylate-silicone rubber copolymer to acrylonitrile-butadiene-acrylate copolymer being 1:1
- Component E-1 resorcinol bis(diphenyl phosphate)
- Component E-2 trimethyl phosphate and diphenyl pentaerythritol diphosphate having a weight ratio of trimethylphosphate to diphenyl pentaerythritol diphosphate being 1:1
- Component F flame-retardant antidrip agent, AS-coated polytetrafluoroethylene system flame-retardant antidrip agent containing 50 wt % polytetrafluoroethylene, on the market
- Component G-1a antioxidant, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite
- Component G-1b antioxidant, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and tris(2,4-di-tert-butylphenyl) phosphite having a weight ratio of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) to tris(2,4-ditert-butylphenyl) phosphite being 1:1
- Component G-2a lubricant, methylenebisstearic acid amide
- Component G-2b lubricant, zinc stearate and silane polymer
- MI Melt Index
- Each of Examples 11 to 14 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- the preparation method of the halogen-free flame-retardant resin composition of each of Examples 11 to 14 included the following steps of:
- the halogen-free flame-retardant resin compositions each of which included recycled PC and recycled PET, prepared as Examples 11 to 14 were, overall, excellent in impact strength and the like, and also excellent in stability of the impact strength (mechanical performance).
- EXAMPLE 11 EXAMPLE 12 EXAMPLE 13 EXAMPLE 14 UNUSED PC A-1a, 5 A-2a, 50 A-1a, 13 A-2a, 25 RECYCLED PC A-3a, 63 A-3b, 20 A-3b, 20 A-3a, 37 RECYCLED PET B-1a, 5 B-1b, 7.5 B-1b, 35 B-1a, 15 STYRENE-ACRYLONITRILE- C-6, 1 C-7, 0.5 C-7, 1 C-6, 1 GLYCIDYL METHACRYLATE TERPOLYMER TOUGHENER D-4, 15 D-5, 5 D-5, 8 D-4, 8 FLAME RETARDANT E-1, 10 E-2, 15 E-2, 20 E-1, 12 FLAME-RETARDANT ANTIDRIP AGENT F, 0.8 F, 0.1 F, 0.5 F, 0.5 ANTIOXIDANT G-1a, 0.1 G-1b, 1 G-1b, 0.5 G-1a, 0.5 LUBRICANT G-2a,
- recycled PET and a styrene-acrylonitrile-glycidyl methacrylate terpolymer (a first mixture) are extruded together to produce a base grain. Consequently, by glycidyl methacrylate, the viscosity of the recycled PET is increased, and the ends thereof are blocked. Accordingly, molecular weights thereof are increased, and distribution of the molecular weights becomes stable, so that ester interchange can be controlled. Accordingly, a halogen-free flame-retardant resin composition including recycled PC and recycled PET of the present invention is excellent in impact strength, has high stability of the impact stretch (mechanical performance), and reduces costs of a product to which the composition is applied.
- each of the obtained pellets (compositions) as Examples 1 to 14 and Comparative Examples 1 to 16 was dried for five hours at 100° C. with a hot-air circulation system dryer. After dried, the pellet was molded at a cylinder temperature of 250° C. and a die temperature of 80° C. by using an injection molding machine (J1300E-C5, produced by The Japan Steel Works, LTD.) to manufacture the copier/printer exterior part 1 shown in FIG. 2 . Then, a sample was extracted from the center thereof. External appearance of each sample was evaluated. The result is shown in TABLE 5 and TABLE 6.
- each sample namely, each product (copier/printer exterior part 1 ) was evaluated by visually observing the external appearance of the sample.
- the criteria are as follows.
- EXAMPLE 1 EXAMPLE 2
- EXAMPLE 3 EXAMPLE 4
- EXAMPLE 5 EXAMPLE 6
- EXTERNAL ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ APPEARANCE EXAMPLE EXAM- EXAMPLE
- EXAMPLE 8 PLE 9 10 11 12 13 14 EXTERNAL ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ APPEARANCE
- the styrene-acrylonitrile-glycidyl methacrylate terpolymer includes 1 wt % to 5 wt % of glycidyl methacrylate and 27 wt % to wt % of acrylonitrile.
- the unused polycarbonate is bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000 to 40000.
- the recycled polycarbonate is bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000 to 40000.
- the recycled polyethylene terephthalate has a viscosity of 0.65 dl/g to 0.9 dl/g.
- the toughener is at least one of a core-shell structured acrylate system toughener, a core-shell structured acrylate-silicone rubber system toughener, a core-shell structured styrene system toughener, a long-chain type toughener, and a reaction type terpolymer toughener.
- the toughener is at least one of a core-shell structured acrylate system toughener and a core-shell structured acrylate-silicone rubber system toughener.
- the core-shell structured acrylate system toughener is a methyl methacrylate-butadiene-styrene copolymer, an acrylonitrile-butadiene-acrylate copolymer, or a methyl methacrylate-butyl methacrylate copolymer
- the core-shell structured acrylate-silicone rubber system toughener is a methyl methacrylate-silicone rubber copolymer
- the core-shell structured styrene system toughener is an acrylonitrile-styrene-butadiene terpolymer
- the long-chain type toughener is an ethylene-methyl acrylate copolymer or an ethylene-butyl acrylate copolymer
- the reaction type terpolymer toughener is an ethylene-methyl acrylate-glycidyl methacrylate copolymer or an ethylene-butyl acrylate-glycidy
- the flame retardant is a phosphate type flame retardant.
- the phosphate type flame retardant is at least one of a monophosphate type flame retardant and an oligophosphate type flame retardant.
- the monophosphate type flame retardant is trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dimethylphenyl phosphate, tributyl phosphate, or xylyl diphenyl phosphate
- the oligophosphate type flame retardant is resorcinol bis (diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or diphenyl pentaerythritol diphosphate.
- the antioxidant is at least one of a hindered phenol system antioxidant and a phosphite system antioxidant.
- the hindered phenol system antioxidant is triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or n-octadecyl-R-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the phosphite system antioxidant is tris (2,4-di-tert-butylphenyl) phosphite or bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite.
- the lubricant is at least one of fatty acid salt, fatty acid amide, a silane polymer, solid paraffin, liquid paraffin, calcium stearate, zinc stearate, octadecanamide, silicone powder, methylene bis(octadecanamide), and N,N′-ethylene bis(octadecanamide).
- the flame-retardant antidrip agent is a polytetrafluoroethylene system flame-retardant antidrip agent.
- the halogen-free flame-retardant resin composition is obtained by: obtaining materials of the halogen-free flame-retardant resin composition; of the materials, sufficiently mixing a recycled polyethylene terephthalate material and a styrene-acrylonitrile-glycidyl methacrylate terpolymer material in a mixer so as to make a first mixture, taking out the first mixture from the mixer, and placing the first mixture in a screw extruder to extrude the first mixture so as to produce a base grain; and sufficiently mixing the base grain and the remaining materials in the mixer so as to make a second mixture, taking out the second mixture from the mixer, and placing the second mixture in the screw extruder to extrude the second mixture so as to produce a final grain as the halogen-free flame-retardant resin composition.
- recycled PET and a styrene-acrylonitrile-glycidyl methacrylate terpolymer namely, a first mixture
- a base grain Consequently, by glycidyl methacrylate, the viscosity of the recycled PET is increased, and the ends thereof are blocked. Accordingly, molecular weights thereof are increased, and distribution of the molecular weights becomes stable, so that ester interchange can be controlled.
- a halogen-free flame-retardant resin composition including recycled PC and recycled PET of the present invention is excellent in impact strength, has high stability of the excellent impact strength (mechanical performance), and reduces costs of a product to which the composition is applied.
- the halogen-free flame-retardant resin composition of the present invention can be applied, for example, to household electric appliance or office automation equipment, so that the halogen-free flame-retardant composition can replace a halogen-free frame-retardant polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) used in the household electric appliance or the office automation equipment.
- PC/ABS halogen-free frame-retardant polycarbonate/acrylonitrile-butadiene-styrene
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Abstract
Description
- 1. Field of the Invention
- The present invention relates to a composition and use of the composition, and, in particular, relates to a halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate and a copier/printer exterior part using the resin composition.
- 2. Description of the Related Art
- With continuous and rapid development of the plastic industry, plastic products have been widely used. At the same time, however, plastic waste has increased, and a huge amount of energy sources has been wasted. Accordingly, collection and reuse of plastic waste has attracted more attention than before.
- Plastic materials are chemicals derived from petroleum. It is well known that petroleum is a lifeline for the industries of the present age and a natural source which cannot be reproduced. According to statics of a related organization, plastic waste generated by one medium-sized city per year can cover plastic materials demanded by 20 small and medium-sized plastics companies per year. Hence, reuse of plastics can be regarded as reuse of petroleum. By melting and granulating plastic waste, supply-demand imbalance in plastic materials can be reduced, and a national budget for petroleum import can be drastically cut.
- Polycarbonate (PC) has excellent impact resistance, heat resistance, dimensional stability, electric insulation and the like, is nontoxic, and has low water absorbency. Accordingly, PC can be used in a wide range of temperatures. In addition, because PC has high light transmittance of 90%, it is named “transparent metal”, and used instead of copper or other colored metals in various fields, such as the electrical and electronic industry, the automobile industry, the mechanical industry, the optical industry, and the pharmaceutical industry. In recent years, consumption of PC has rapidly and continuously increased, and unavoidably, a large amount of PC waste has been generated. PC waste is an important recycled source, and it is necessary to properly process PC waste so as to reduce influence of PC waste on environments. Collection and reuse of PC waste contribute to economic and social benefits significantly. Examples of PC waste to be collected include PC used in buckets, dies, and optical disks.
- According to data by PCi (PET Packaging, Resin & Recycling Ltd), in 2008, production capacity of polyethylene terephthalate (PET) in the world reached 67 million tons, and output thereof was 61 million tons. Meanwhile, several million tons of PET waste, which is generated by consumption of a large amount of PET, is generated every year. If PET waste is not sufficiently used, a large amount of resources is wasted. Nowadays, recycled PET is mainly used in fibers, sheets, and bottles for containing nonfood, and used in some plastic bottles, monofilaments, and the like. However, the application range of recycled PET is relatively narrow in the engineering plastic field. In particular, application thereof in the plastic alloy field is hardly reported.
- In U.S. Pat. No. 436,078, there is disclosed selectively separating PET from PET waste such as PET bottles by using a solvent, and collecting the PET (recycled PET) so as to recycle the PET. Furthermore, in Chinese Patent Application Laid-Open Publication No. 101338070, there is disclosed preparing a composition containing flame-retardant PC and a polyester resin, which are denaturalized by an epoxy group-containing rubber modified aromatic vinyl copolymer resin, but not disclosed using a recycled material.
- Engineering PET has low viscosity/toughness in general, and recycled PET has lower viscosity/toughness. Hence, unless the viscosity/toughness is increased, the application range of recycled PET is not widened. Furthermore, influence of low molecular weights and wide distribution of molecular weights of recycled PET on performance thereof is more than that of recycled PC on performance thereof, and hence a composition including recycled PET and a product using the composition are unstable in performance, and difficult to obtain stable mechanical performance. Consequently, the application range of recycled PET is somewhat limited.
- Therefore, development of a halogen-free flame-retardant resin composition including recycled PET and recycled PC and a product using the resin composition has an important meaning in terms of environmental protection and practical application.
- The present invention is made in view of the circumstances, and objects of the present invention include providing a halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate and a copier/printer exterior part using the resin composition, each of which can realize cycle use (recycling) of polycarbonate and polyethylene terephthalate, and prevent stability of mechanical performance of materials (components) of the resin composition from decreasing.
- In order to achieve at least one of the objects, according to an aspect of the present invention, there is provided a copier/printer exterior part using a halogen-free flame-retardant resin composition including: 5 wt % to 50 wt % of unused polycarbonate; 20 wt % to 63 wt % of recycled polycarbonate; 5 wt % to 35 wt % of recycled polyethylene terephthalate; 0.2 wt % to 2 wt % of a styrene-acrylonitrile-glycidyl methacrylate terpolymer; 5 wt % to 15 wt % of a toughener; 10 wt % to 20 wt % of a flame retardant; 0.1 wt % to 0.8 wt % of a flame-retardant antidrip agent; 0.1 wt % to 1 wt % of an antioxidant; and 0.1 wt % to 2 wt % of a lubricant, wherein the styrene-acrylonitrile-glycidyl methacrylate terpolymer includes 1 wt % to 5 wt % of glycidyl methacrylate and wt % to 33 wt % of acrylonitrile.
- The present invention is fully understood from the detailed description given hereinafter and the accompanying drawings, which are given by way of illustration only, and thus are not intended to limit the present invention, wherein:
-
FIG. 1 shows external appearance of a copier using an exterior part in accordance with an example of the present invention; and -
FIG. 2 is a perspective view of the exterior part (outside dimensions: length of 500 mm, width of 600 mm, and thickness of 2.5 mm) using a resin composition in accordance with an example of the present invention. - In the following, the present invention is described in detail by using examples. The examples are given for a person skilled in the art only to more easily understand the present invention. Hence the present invention is not limited to the examples, and can be variously modified without departing from the scope of the present invention.
- An exterior part for a copier or a printer (a copier/printer
exterior part 1 shown inFIG. 2 ) of the present invention is used in a scanner which reads an original document, a copier which prints the original document read by the scanner, a printer or a facsimile apparatus which prints image data inputted from an external apparatus, or a multifunctional machine called MFP (Multi Function Peripheral) which has these functions. The copier/printerexterior part 1 of the present invention is used for exterior parts G1 to G9 of a copier shown inFIG. 1 , for example. The copier/printerexterior part 1 is provided withpin side gates 2 as shown inFIG. 2 . - In the following, an “unused” component indicates that the component has not been used yet, and a “recycled” component indicates that the component has been used before. That is, for example, “unused polycarbonate (PC)” indicates that the PC has not been used, and “recycled polycarbonate (PC)” indicates that the PC has been used before. These are well known by a person skilled in the art.
- Component A-1: unused PC having a weight average molecular weight of 25000, produced by HONAM Petrochemical Corp.
- Component A-2: unused PC having a weight average molecular weight of 21000, produced by HONAM Petrochemical Corp.
- Component A-3: recycled PC having a weight average molecular weight of 24000, on the market
- Component B-1: recycled PET derived from PET bottles/sheets for drinks, and having a viscosity of 0.8 dl/g, on the market
- Component B-2: unused PET having a viscosity of 1.0 dl/g, produced by Jinshan Petrochemical Company
- Component C-1: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 8 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-2: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 5 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-3: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-3a: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 35 wt % acrylonitrile
- Component C-3b: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 30 wt % acrylonitrile
- Component C-3c: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 27 wt % acrylonitrile
- Component C-3d: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 20 wt % acrylonitrile
- Component C-3e: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 15 wt % acrylonitrile
- Component C-4: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 1 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component C-5: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 0.5 wt % glycidyl methacrylate and 28 wt % acrylonitrile
- Component D-1: MBS EM-500, produced by LG Electronics
- Component D-2: acrylic acid-silicone rubber system toughener, S-2001, produced by Mitsubishi Rayon Co., Ltd.
- Component D-3: acrylonitrile-butadiene-styrene copolymer toughener containing 54 wt % butadiene, 34 wt % styrene and 12 wt % acrylonitrile, produced by Korea Kumho Petrochemical Co., Ltd.
- Component E: flame retardant, BDP, produced by Great Lakes Chemical Corporation
- Component F: flame-retardant antidrip agent, AS-coated polytetrafluoroethylene system flame-retardant antidrip agent containing 50 wt % polytetrafluoroethylene, on the market
- Component G: processing aid containing, for example, ethylenebisstearamide (lubricant), IRGAFOS®168 (phosphite (phosphoric acid ester) system antioxidant), IRGANOX®1076 (hindered phenol system antioxidant), and DOW CORNING® MB-50 (lubricant), and having a weight ratio of ethylenebisstearamide, IRGAFOS®168, IRGANOX®1076 and DOW CORNING® MB-50 being 2:2:1:1
- Notched Izod Impact Strength: measured in accordance with ASTM-D256 standard
- MI (Melt Index): measured in accordance with ASTM-D1238 standard
- FR (Flame Resistance): measured in accordance with UL 94 standard
- Each of Examples 1 to 10 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- The preparation method of the halogen-free flame-retardant resin composition of each of Examples 1 to 10 included the following steps of:
- a) obtaining materials of the halogen-free flame-retardant resin composition in accordance with the components and their contents (wt %) shown in TABLE 1;
- b) of the materials obtained at Step (a), sufficiently mixing a recycled PET material and a styrene-acrylonitrile-glycidyl methacrylate terpolymer material in a mixer so as to make a first mixture, taking out the first mixture from the mixer, and placing the first mixture in a screw extruder to extrude the first mixture so as to produce a base grain (a first step in a two-step method as a processing method); and
- c) sufficiently mixing the base grain and the remaining materials in the mixer so as to make a second mixture, taking out the second mixture from the mixer, and placing the second mixture in the screw extruder to extrude the second mixture so as to produce a final grain as the halogen-free flame-retardant resin composition (pellet) (a second step in the two-step method as the processing method).
- The mechanical performance of each obtained pellet was examined. The result is shown in TABLE 1.
- Each of Comparative Examples 1, 2, 8 and 9 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- The preparation method of the halogen-free flame-retardant resin composition of each of Comparative Examples 1, 2, 8 and 9 included the following steps of:
- a) obtaining materials of the halogen-free flame-retardant resin composition in accordance with the components and their contents (wt %) shown in TABLE 2; and
- b) sufficiently mixing the materials in a mixer so as to make a mixture, taking out the mixture from the mixer, and placing the mixture in a screw extruder to extrude the mixture so as to produce a grain as the halogen-free flame-retardant resin composition (pellet) (a one-step method as the processing method).
- The mechanical performance of each obtained pellet was examined. The result is shown in TABLE 2.
- Each of Comparative Examples 3 to 7 and 10 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- The preparation method of the halogen-free flame-retardant resin composition of each of Comparative Examples 3 to 7 and 10 included the following steps of
- a) obtaining materials of the halogen-free flame-retardant resin composition in accordance with the components and their contents (wt %) shown in TABLE 2;
- b) of the materials obtained at Step (a), sufficiently mixing a recycled PET material and a styrene-acrylonitrile-glycidyl methacrylate terpolymer material in a mixer so as to make a first mixture, taking out the first mixture from the mixer, and placing the first mixture in a screw extruder to extrude the first mixture so as to produce a base grain (the first step in the two-step method as the processing method); and
- c) sufficiently mixing the base grain and the remaining materials in the mixer so as to make a second mixture, taking out the second mixture from the mixer, and placing the second mixture in the screw extruder to extrude the second mixture so as to produce a final grain as the halogen-free flame-retardant resin composition (pellet) (the second step in the two-step method as the processing method).
- The mechanical performance of each obtained pellet was examined. The result is shown in TABLE 2.
- Each of Comparative Examples 11 to 16 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- The preparation method of the halogen-free flame-retardant resin composition of each of Comparative Examples 11 to 16 included the following steps of
- a) obtaining materials of the halogen-free flame-retardant resin composition in accordance with the components and their contents (wt %) shown in TABLE 3;
- b) of the materials obtained at Step (a), sufficiently mixing a recycled PET material and a styrene-acrylonitrile-glycidyl methacrylate terpolymer material in a mixer so as to make a first mixture, taking out the first mixture from the mixer, and placing the first mixture in a screw extruder to extrude the first mixture so as to produce a base grain (the first step in the two-step method as the processing method); and
- c) sufficiently mixing the base grain and the remaining materials in the mixer so as to make a second mixture, taking out the second mixture from the mixer, and placing the second mixture in the screw extruder to extrude the second mixture so as to produce a final grain as the halogen-free flame-retardant resin composition (pellet) (the second step in the two-step method as the processing method).
- The mechanical performance of each obtained pellet was examined. The result is shown in TABLE 3.
- 1.4.1 It is Preferable that the Styrene-Acrylonitrile-Glycidyl Methacrylate Terpolymer Contain 1 wt % to 5 wt % Glycidyl Methacrylate and 27 wt % to 30 wt % Acrylonitrile.
(1) When Example 1 was compared with Comparative Examples 3 and 4, as shown in TABLE 1 and TABLE 2, the notched Izod impact strength (“impact strength” hereinafter) of Comparative Examples 3 and 4 was significantly lower than that of Example 1. The difference between Example 1 and Comparative Examples 3 and 4 was the component C. That is, Example 1, Comparative Example 3 and Comparative Example 4 used the components C-3, C-1 and C-5, respectively. Each of the components C-3, C-1 and C-5 was a styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 28 wt % acrylonitrile. However, the components C-3 (Example 1), C-1 (Comparative Example 3) and C-5 (Comparative Example 4) contained 2 wt %, 8 wt % and 0.5 wt % glycidyl methacrylate, respectively. Therefore, it is indicated that the halogen-free flame-retardant resin composition which contains the styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate is excellent in mechanical performance.
(2) When Example 1 was compared with Examples 5 and 6, as shown in TABLE 1, the impact strength of Examples 1, 5 and 6 was high. Examples 1, 5 and 6 used the components C-3, C-2 and C-4, respectively. Each of the components C-3, C-2 and C-4 was a styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 28 wt % acrylonitrile. However, the components C-3 (Example 1), C-2 (Example 5) and C-4 (Example 6) contained 2 wt %, 5 wt % and 1 wt % glycidyl methacrylate, respectively. Therefore, it is preferable that the component, namely, the styrene-acrylonitrile-glycidyl methacrylate terpolymer, contain 1 wt % to 5 wt % glycidyl methacrylate.
(3) When Example 1 was compared with Comparative Examples 11, 12, 13, 14 and 15, as shown in TABLE 1 and TABLE 3, the impact strength of Example 1 was high, and the impact strength of Comparative Examples 12 and 13 was relatively high too. The difference between Example 1 and Comparative Examples 11, 12, 13, 14 and 15 was the content (wt %) of acrylonitrile in the styrene-acrylonitrile-glycidyl methacrylate terpolymer (component C-3, C-3a, C-3b, C-3c, C-3d or C-3e). The contents of acrylonitrile of the components C-3 (Example 1), C-3a (Comparative Example 11), C-3b (Comparative Example 12), C-3c (Comparative Example 13), C-3d (Comparative Example 14) and C-3e (Comparative Example 15) were 28 wt %, 35 wt %, 30 wt %, 27 wt %, 20 wt % and 15 wt %, respectively. Therefore, it is preferable that the component, namely, the styrene-acrylonitrile-glycidyl methacrylate terpolymer, contain 27 wt % to 30 wt % acrylonitrile. - In conclusion, when a styrene-acrylonitrile-glycidyl methacrylate terpolymer is used in the halogen-free flame-retardant resin composition, it is preferable that the terpolymer contain 1 wt % to 5 wt % glycidyl methacrylate and 27 wt % to 30 wt % acrylonitrile.
- 1.4.2 It is Preferable that the Halogen-Free Flame-Retardant Resin Composition Contain 0.2 wt % to 2 wt % Styrene-Acrylonitrile-Glycidyl Methacrylate Terpolymer.
- When Examples 1, 7 and 8 were compared with each other, as shown in TABLE 1, “Example 8>Example 1>Example 7” was true in impact strength.
- The difference between Examples 1, 7 and 8 was the content of the component C-3. The contents of the component C-3 of Examples 1, 7 and 8 were 0.4 wt %, 0.2 wt % and 2 wt %, respectively.
- When Comparative Examples 6 and 7 were compared with each other, as shown in TABLE 2, the impact strength of Comparative Example 6 was significantly lower than that of Comparative Example 7. When Comparative Example 7 and Example 8 were compared with each other, as shown in TABLE 2 and TABLE 1, the impact strength of Comparative Example 7 was almost the same as that of Example 8. However, the melt index of Comparative Example 7 was lower than that of Example 8. That is, the melt index decreased as the content of the styrene-acrylonitrile-glycidyl methacrylate terpolymer increased.
- Furthermore, when Comparative Examples 1 and 2 were compared with each other, as shown in TABLE 2, “Comparative Example 2>Comparative Example 1” was true in impact strength. This indicates that the styrene-acrylonitrile-glycidyl methacrylate terpolymer is very important in the halogen-free flame-retardant resin composition, and can ensure impact strength to some extent. In addition, when the content of the styrene-acrylonitrile-glycidyl methacrylate terpolymer was less than 0.2 wt %, the styrene-acrylonitrile-glycidyl methacrylate terpolymer did not exert the favorable influence on the impact strength much. On the other hand, when the content thereof was more than 2 wt %, the impact strength did not improve any more, but the liquidity still decreased.
- In conclusion, it is preferable that the halogen-free flame-retardant resin composition contain 0.2 wt % to 2 wt % styrene-acrylonitrile-glycidyl methacrylate terpolymer.
- 1.4.3 It is Preferable that the Halogen-Free Flame-Retardant Resin Composition is Prepared by Using the Two-Step Method as the Processing Method.
- When Examples 1, 9 and 10 were compared with Comparative Examples 1, 8 and 9, as shown in TABLE 1 and TABLE 2, the impact strength of Examples 1, 9 and 10 was higher than that of Comparative Examples 1, 8 and 9. This is because, as the processing method, Examples 1, 9 and 10 used the two-step method while Comparative Examples 1, 8 and 9 used the one-step method. This indicates that the composition prepared by using the two-step method as the processing method is excellent in impact strength, and indicates that it is important to increase the viscosity of recycled PET in advance in order to stabilize physical property thereof.
- 1.4.4 It is Preferable that the Halogen-Free Flame-Retardant Resin Composition Contains Less than 30 wt % Recycled PET.
- When Examples 1, 9 and 10 were compared with Comparative Examples 1, 8, and 9, as shown in TABLE 1 and TABLE 2, the higher the content of recycled PET was, the lower the impact strength was. In addition, when the content of recycled PET was 30 wt % (or more), the flame resistance became poor.
- Furthermore, when Example 10 was compared with Comparative Example 10, as shown in TABLE 1 and TABLE 2, the impact strength of Comparative Example 10 was significantly lower than that of Example 10. The difference between Example and Comparative Example 10 was the content of recycled PET. This indicates that, if the halogen-free flame-retardant resin composition contains more than 30 wt % recycled PET, the impact strength significantly decreases, and may exert a bad influence on the composition in terms of practical application.
- In conclusion, it is preferable that, in terms of impact strength and flame resistance, the halogen-free flame-retardant resin composition contain less than 30 wt % recycled PET.
- When Example 1 was compared with Comparative Example 16, as shown in TABLE 1 and TABLE 3, “Example 1>Comparative Example 16” was true in impact strength. The difference between Example 1 and Comparative Example 16 was PET. Example 1 used recycled PET, and the recycled PET had been processed by the component C-3, while Comparative Example 16 used unused PET having a high viscosity. This indicates that even if unused PET is used as PET in the halogen-free flame-retardant resin composition, physical property of the PET (the composite, by extension) varies, and indicates that the styrene-acrylonitrile-glycidyl methacrylate terpolymer is effective not only in increasing the viscosity of PET (recycled PET), but also in preventing ester interchange of the PET, by blocking the ends of the PET.
- When Example 1 was compared with Example 4, as shown in TABLE 1, the impact strength of Example 1 was almost the same as that of Example 4. This indicates that the influence of the content of recycled PC on the impact strength can be controlled.
- When Examples 1, 2 and 3 were compared with each other, as shown in TABLE 1, the impact strength thereof was almost the same. The difference between Examples 1, 2 and 3 was the toughener. Examples 1, 2 and 3 used, as the toughener, the components D1, D2 and D3, which is a mixture of the components D1 and D2, respectively. This indicates that both the core-shell structured acrylate system toughener and the core-shell structured acrylate-silicone rubber system toughener are relatively effective in toughening the composition.
-
TABLE 1 EXAMPLE EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- PLE 1 PLE 2 PLE 3 PLE 4 PLE 5 PLE 6 PLE 7 PLE 8 PLE 9 PLE 10 COMPONENT 16 16 16 3 16 16 16 15 12.4 10 A-1 COMPONENT 16.5 16.5 16.5 3.5 16.5 16.5 16.5 15.9 13 10.2 A-2 COMPONENT 32.5 32.5 32.5 58.5 32.5 32.5 32.5 32.5 25.4 20.2 A-3 COMPONENT 10 10 10 10 10 10 10 10 20 30 B-1 COMPONENT B-2 COMPONENT C-1 COMPONENT 0.4 C-2 COMPONENT 0.4 0.4 0.4 0.4 0.2 2 1 1.4 C-3 COMPONENT 0.4 C-4 COMPONENT C-5 COMPONENT 8.9 5 8.9 8.9 8.9 9.1 8.9 11.9 14.8 D-1 COMPONENT 8.9 D-2 COMPONENT 3.9 D-3 COMPONENT E 14.4 14.4 14.4 14.4 14.4 14.4 14.4 14.4 14.9 12.4 COMPONENT F 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.4 COMPONENT G 1 1 1 1 1 1 1 1 1 1 PROCESSING TWO- TWO- TWO- TWO- TWO- TWO-STEP TWO-STEP TWO-STEP TWO-STEP TWO-STEP METHOD STEP STEP STEP STEP STEP METHOD METHOD METHOD METHOD METHOD METHOD METHOD METHOD METHOD METHOD NOTCHED 532.6 541.6 489.3 527.9 542.1 562.3 356.5 554.4 455.7 334.7 IZOD IMPACT STRENGTH [J/m], ⅛ in MI [g/10 min], 27.5 28.2 27.5 28.6 27.8 27.2 28.2 25.2 35.2 41.3 265° C. × 2.16 kg FR, 1/16 in V0 V0 V0 V0 V0 V0 V0 V0 V0 V2 -
TABLE 2 COMPARATIVE EXAMPLE COM- COM- COM- COM- COM- COM- COM- COM- COM- COM- PARA- PARA- PARA- PARA- PARA- PARA- PARA- PARA- PARA- PARA- TIVE TIVE TIVE TIVE TIVE TIVE TIVE TIVE TIVE TIVE EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- PLE 1 PLE 2 PLE 3 PLE 4 PLE 5 PLE 6 PLE 7 PLE 8 PLE 9 PLE 10 COMPONENT 16 16 16 16 32.5 16 15 12.4 10 8.6 A-1 COMPONENT 16.7 16.5 16.5 16.5 32.5 16.5 15.7 13 10.2 9 A-2 COMPONENT 32.7 32.5 32.5 32.5 32.5 32.5 25.4 20.2 17.6 A-3 COMPONENT 10 10 10 10 10 10 10 20 30 33 B-1 COMPONENT B-2 COMPONENT 0.4 C-1 COMPONENT C-2 COMPONENT 0.4 0.4 0.1 2.2 1 1.4 1.6 C-3 COMPONENT C-4 COMPONENT 0.4 C-5 COMPONENT 8.9 8.9 8.9 8.9 8.9 9.2 8.9 11.9 14.8 16.8 D-1 COMPONENT D-2 COMPONENT D-3 COMPONENT E 14.4 14.4 14.4 14.4 14.4 14.4 14.4 14.9 12.4 12.4 COMPONENT F 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.4 COMPONENT G 1 1 1 1 1 1 1 1 1 1 PROCESSING ONE- ONE- TWO- TWO- TWO- TWO- TWO- ONE- ONE- TWO- METHOD STEP STEP STEP STEP STEP STEP STEP STEP STEP STEP METHOD METHOD METHOD METHOD METHOD METHOD METHOD METHOD METHOD METHOD NOTCHED 138.7 258.7 182.5 212.3 572.6 152.1 532.1 95.6 78.6 119.3 IZOD IMPACT STRENGTH [J/m], ⅛ in MI [g/10 min], 30.6 25.6 28.5 28.9 27.8 30.9 24.9 35.6 39.3 43.2 265° C. × 2.16 kg FR, 1/16 in V0 V0 V0 V0 V0 V0 V0 V0 V2 V2 -
TABLE 3 COMPARATIVE EXAMPLE COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE EXAMPLE 11 EXAMPLE 12 EXAMPLE 13 EXAMPLE 14 EXAMPLE 15 EXAMPLE 16 COMPONENT A-1 16 16 16 16 16 16 COMPONENT A-2 16.5 16.5 16.5 16.5 16.5 16.5 COMPONENT A-3 32.5 32.5 32.5 32.5 32.5 32.5 COMPONENT B-1 10 10 10 10 10 COMPONENT B-2 10 COMPONENT C-1 0.4 COMPONENT C-3a 0.4 COMPONENT C-3b 0.4 COMPONENT C-3c 0.4 COMPONENT C-3d 0.4 COMPONENT C-3e 0.4 COMPONENT D-1 8.9 8.9 8.9 8.9 8.9 9.3 COMPONENT E 14.4 14.4 14.4 14.4 14.4 14.4 COMPONENT F 0.3 0.3 0.3 0.3 0.3 0.3 COMPONENT G 1 1 1 1 1 1 PROCESSING TWO-STEP TWO-STEP TWO-STEP TWO-STEP TWO-STEP TWO-STEP METHOD METHOD METHOD METHOD METHOD METHOD METHOD NOTCHED 334.2 451.1 466.2 241.5 231.5 335.3 IZOD IMPACT STRENGTH [J/m], ⅛ in MI [g/10 min], 265° C. × 2.16 kg 26.8 27.2 28.1 28.5 28.9 26.5 FR, 1/16 in V0 V0 V0 V0 V0 V0 - Component A-1a: Unused PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000
- Component A-2a: Unused PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 40000
- Component A-3a: Recycled PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000
- Component A-3b: Recycled PC, bisphenol A type aromatic polycarbonate having a weight average molecular weight of 40000
- Component B-1a: Recycled PET having a viscosity of 0.65 dl/g, on the market
- Component B-1b: Recycled PET having a viscosity of 0.90 dl/g, on the market
- Component C-6: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 2 wt % glycidyl methacrylate and 33 wt % acrylonitrile, produced in-house
- Component C-7: styrene-acrylonitrile-glycidyl methacrylate terpolymer containing 3 wt % glycidyl methacrylate and 20 wt % acrylonitrile, produced in-house
- Component D-4: ethylene-methyl acrylate copolymer and ethylene-methyl acrylate-glycidyl methacrylate copolymer having a weight ratio of ethylene-methyl acrylate copolymer to ethylene-methyl acrylate-glycidyl methacrylate copolymer being 1:1
- Component D-5: methyl methacrylate-silicone rubber copolymer and acrylonitrile-butadiene-acrylic ester copolymer having a weight ratio of methyl methacrylate-silicone rubber copolymer to acrylonitrile-butadiene-acrylate copolymer being 1:1
- Component E-1: resorcinol bis(diphenyl phosphate)
- Component E-2: trimethyl phosphate and diphenyl pentaerythritol diphosphate having a weight ratio of trimethylphosphate to diphenyl pentaerythritol diphosphate being 1:1
- Component F: flame-retardant antidrip agent, AS-coated polytetrafluoroethylene system flame-retardant antidrip agent containing 50 wt % polytetrafluoroethylene, on the market
- Component G-1a: antioxidant, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite
- Component G-1b: antioxidant, pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) and tris(2,4-di-tert-butylphenyl) phosphite having a weight ratio of pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) to tris(2,4-ditert-butylphenyl) phosphite being 1:1
- Component G-2a: lubricant, methylenebisstearic acid amide
- Component G-2b: lubricant, zinc stearate and silane polymer
- Notched Izod Impact Strength: measured in accordance with ASTM-D256 standard
- MI (Melt Index): measured in accordance with ASTM-D1238 standard
- FR (Flame Resistance): measured in accordance with UL 94 standard
- Each of Examples 11 to 14 provided a halogen-free flame-retardant resin composition including recycled PC and recycled PET.
- The preparation method of the halogen-free flame-retardant resin composition of each of Examples 11 to 14 included the following steps of:
- a) obtaining materials of the halogen-free flame-retardant resin composition in accordance with the components and their contents (wt %) shown in TABLE 4;
- b) of the materials, sufficiently mixing a recycled polyethylene terephthalate material and a styrene-acrylonitrile-glycidyl methacrylate terpolymer material in a mixer so as to make a first mixture, taking out the first mixture from the mixer, and placing the first mixture in a screw extruder to extrude the first mixture so as to produce a base grain (the first step in the two-step method as the processing method); and
- c) sufficiently mixing the base grain and the remaining materials in the mixer so as to make a second mixture, taking out the second mixture from the mixer, and placing the second mixture in the screw extruder to extrude the second mixture so as to produce a final grain as the halogen-free flame-retardant resin composition (pellet) (the second step in the two-step method as the processing method).
- The mechanical performance of each obtained pellet was examined. The result is shown in TABLE 4.
- As shown in TABLE 4, the halogen-free flame-retardant resin compositions, each of which included recycled PC and recycled PET, prepared as Examples 11 to 14 were, overall, excellent in impact strength and the like, and also excellent in stability of the impact strength (mechanical performance).
-
TABLE 4 EXAMPLE EXAMPLE 11 EXAMPLE 12 EXAMPLE 13 EXAMPLE 14 UNUSED PC A-1a, 5 A-2a, 50 A-1a, 13 A-2a, 25 RECYCLED PC A-3a, 63 A-3b, 20 A-3b, 20 A-3a, 37 RECYCLED PET B-1a, 5 B-1b, 7.5 B-1b, 35 B-1a, 15 STYRENE-ACRYLONITRILE- C-6, 1 C-7, 0.5 C-7, 1 C-6, 1 GLYCIDYL METHACRYLATE TERPOLYMER TOUGHENER D-4, 15 D-5, 5 D-5, 8 D-4, 8 FLAME RETARDANT E-1, 10 E-2, 15 E-2, 20 E-1, 12 FLAME-RETARDANT ANTIDRIP AGENT F, 0.8 F, 0.1 F, 0.5 F, 0.5 ANTIOXIDANT G-1a, 0.1 G-1b, 1 G-1b, 0.5 G-1a, 0.5 LUBRICANT G-2a, 0.1 G-2b, 0.9 G-2b, 2 G-2a, 1 PROCESSING METHOD TWO-STEP TWO-STEP TWO-STEP TWO-STEP METHOD METHOD METHOD METHOD NOTCHED IZOD IMPACT STRENGTH [J/m], ⅛ in 289.3 614.3 112.1 346.5 MI [g/10 min], 265° C. × 2.16 kg 23.9 19.3 46.5 35.5 FR, 1/16 in N/A V0 N/A V2 - As described above, in the present invention, recycled PET and a styrene-acrylonitrile-glycidyl methacrylate terpolymer (a first mixture) are extruded together to produce a base grain. Consequently, by glycidyl methacrylate, the viscosity of the recycled PET is increased, and the ends thereof are blocked. Accordingly, molecular weights thereof are increased, and distribution of the molecular weights becomes stable, so that ester interchange can be controlled. Accordingly, a halogen-free flame-retardant resin composition including recycled PC and recycled PET of the present invention is excellent in impact strength, has high stability of the impact stretch (mechanical performance), and reduces costs of a product to which the composition is applied.
- Each of the obtained pellets (compositions) as Examples 1 to 14 and Comparative Examples 1 to 16 was dried for five hours at 100° C. with a hot-air circulation system dryer. After dried, the pellet was molded at a cylinder temperature of 250° C. and a die temperature of 80° C. by using an injection molding machine (J1300E-C5, produced by The Japan Steel Works, LTD.) to manufacture the copier/
printer exterior part 1 shown inFIG. 2 . Then, a sample was extracted from the center thereof. External appearance of each sample was evaluated. The result is shown in TABLE 5 and TABLE 6. - The evaluation on the external appearance of each sample, namely, each product (copier/printer exterior part 1), was evaluated by visually observing the external appearance of the sample. The criteria are as follows.
- ⊚ (double circle):
-
- There is no problem on the external appearance.
- ◯ (circle):
-
- Burned spots and/or burrs are slightly seen, but they are not a problem as a product.
- X (cross):
-
- Burned spots and/or burrs are seen, and they are a problem as a product.
-
TABLE 5 EXAMPLE EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE 4 EXAMPLE 5 EXAMPLE 6 EXTERNAL ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ APPEARANCE EXAMPLE EXAM- EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE EXAMPLE 7 EXAMPLE 8 PLE 9 10 11 12 13 14 EXTERNAL ⊚ ⊚ ◯ ⊚ ⊚ ⊚ ⊚ ⊚ APPEARANCE -
TABLE 6 COMPARATIVE EXAMPLE COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE COMPARATIVE EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 EXAMPLE 4 EXAMPLE 5 EXAMPLE 6 EXTERNAL ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ APPEARANCE COMPARATIVE EXAMPLE COM- COM- COM- COM- COM- COM- COM- COM- PARA- PARA- PARA- PARA- PARA- PARA- PARA- PARA- TIVE TIVE TIVE TIVE TIVE TIVE TIVE TIVE EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- EXAM- COMPARATIVE COMPARATIVE PLE 7 PLE 8 PLE 9 PLE 10 PLE 11 PLE 12 PLE 13 PLE 14 EXAMPLE 15 EXAMPLE 16 EXTERNAL X ◯ ◯ X ◯ ◯ ◯ ◯ ◯ ◯ APPEARANCE - When Examples 1 to 14 were compared with Comparative Examples 1 to 16, as shown in TABLE 5 and TABLE 6, the copier/
printer exterior parts 1 manufactured by using the compositions of Examples 1 to 14 were better in external appearance. - According to an aspect of the examples of the present invention, there is provided a copier/printer exterior part using a halogen-free flame-retardant resin composition including: 5 wt % to 50 wt % of unused polycarbonate; 20 wt % to 63 wt % of recycled polycarbonate; 5 wt % to 35 wt % of recycled polyethylene terephthalate; 0.2 wt % to 2 wt % of a styrene-acrylonitrile-glycidyl methacrylate terpolymer; 5 wt % to 15 wt % of a toughener; 10 wt % to 20 wt % of a flame retardant; 0.1 wt % to 0.8 wt % of a flame-retardant antidrip agent; 0.1 wt % to 1 wt % of an antioxidant; and 0.1 wt % to 2 wt % of a lubricant, wherein the styrene-acrylonitrile-glycidyl methacrylate terpolymer includes 1 wt % to 5 wt % of glycidyl methacrylate and wt % to 33 wt % of acrylonitrile.
- Preferably, in the copier/printer exterior part, the styrene-acrylonitrile-glycidyl methacrylate terpolymer includes 1 wt % to 5 wt % of glycidyl methacrylate and 27 wt % to wt % of acrylonitrile.
- Preferably, in the copier/printer exterior part, the unused polycarbonate is bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000 to 40000.
- Preferably, in the copier/printer exterior part, the recycled polycarbonate is bisphenol A type aromatic polycarbonate having a weight average molecular weight of 10000 to 40000.
- Preferably, in the copier/printer exterior part, the recycled polyethylene terephthalate has a viscosity of 0.65 dl/g to 0.9 dl/g.
- Preferably, in the copier/printer exterior part, the toughener is at least one of a core-shell structured acrylate system toughener, a core-shell structured acrylate-silicone rubber system toughener, a core-shell structured styrene system toughener, a long-chain type toughener, and a reaction type terpolymer toughener.
- Preferably, in the copier/printer exterior part, the toughener is at least one of a core-shell structured acrylate system toughener and a core-shell structured acrylate-silicone rubber system toughener.
- Preferably, in the copier/printer exterior part, the core-shell structured acrylate system toughener is a methyl methacrylate-butadiene-styrene copolymer, an acrylonitrile-butadiene-acrylate copolymer, or a methyl methacrylate-butyl methacrylate copolymer, the core-shell structured acrylate-silicone rubber system toughener is a methyl methacrylate-silicone rubber copolymer, the core-shell structured styrene system toughener is an acrylonitrile-styrene-butadiene terpolymer, the long-chain type toughener is an ethylene-methyl acrylate copolymer or an ethylene-butyl acrylate copolymer, and the reaction type terpolymer toughener is an ethylene-methyl acrylate-glycidyl methacrylate copolymer or an ethylene-butyl acrylate-glycidyl methacrylate copolymer.
- Preferably, in the copier/printer exterior part, the flame retardant is a phosphate type flame retardant.
- Preferably, in the copier/printer exterior part, the phosphate type flame retardant is at least one of a monophosphate type flame retardant and an oligophosphate type flame retardant.
- Preferably, in the copier/printer exterior part, the monophosphate type flame retardant is trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dimethylphenyl phosphate, tributyl phosphate, or xylyl diphenyl phosphate, and the oligophosphate type flame retardant is resorcinol bis (diphenyl phosphate), bisphenol A bis(diphenyl phosphate), or diphenyl pentaerythritol diphosphate.
- Preferably, in the copier/printer exterior part, the antioxidant is at least one of a hindered phenol system antioxidant and a phosphite system antioxidant.
- Preferably, in the copier/printer exterior part, the hindered phenol system antioxidant is triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], or n-octadecyl-R-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the phosphite system antioxidant is tris (2,4-di-tert-butylphenyl) phosphite or bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite.
- Preferably, in the copier/printer exterior part, the lubricant is at least one of fatty acid salt, fatty acid amide, a silane polymer, solid paraffin, liquid paraffin, calcium stearate, zinc stearate, octadecanamide, silicone powder, methylene bis(octadecanamide), and N,N′-ethylene bis(octadecanamide).
- Preferably, in the copier/printer exterior part, the flame-retardant antidrip agent is a polytetrafluoroethylene system flame-retardant antidrip agent.
- Preferably, in the copier/printer exterior part, the halogen-free flame-retardant resin composition is obtained by: obtaining materials of the halogen-free flame-retardant resin composition; of the materials, sufficiently mixing a recycled polyethylene terephthalate material and a styrene-acrylonitrile-glycidyl methacrylate terpolymer material in a mixer so as to make a first mixture, taking out the first mixture from the mixer, and placing the first mixture in a screw extruder to extrude the first mixture so as to produce a base grain; and sufficiently mixing the base grain and the remaining materials in the mixer so as to make a second mixture, taking out the second mixture from the mixer, and placing the second mixture in the screw extruder to extrude the second mixture so as to produce a final grain as the halogen-free flame-retardant resin composition.
- According to the present invention, recycled PET and a styrene-acrylonitrile-glycidyl methacrylate terpolymer, namely, a first mixture, are extruded to produce a base grain. Consequently, by glycidyl methacrylate, the viscosity of the recycled PET is increased, and the ends thereof are blocked. Accordingly, molecular weights thereof are increased, and distribution of the molecular weights becomes stable, so that ester interchange can be controlled. Accordingly, a halogen-free flame-retardant resin composition including recycled PC and recycled PET of the present invention is excellent in impact strength, has high stability of the excellent impact strength (mechanical performance), and reduces costs of a product to which the composition is applied.
- The halogen-free flame-retardant resin composition of the present invention can be applied, for example, to household electric appliance or office automation equipment, so that the halogen-free flame-retardant composition can replace a halogen-free frame-retardant polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) used in the household electric appliance or the office automation equipment.
- This application is based upon and claims the benefit of priority under 35 USC 119 of Chinese Patent Application No. 201210016861.X filed Jan. 18, 2012, the entire disclosure of which, including the description, claims, drawings, and abstract, is incorporated herein by reference in its entirety.
Claims (16)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14/302,633 US8865795B1 (en) | 2012-01-18 | 2014-06-12 | Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210016861.XA CN103214808B (en) | 2012-01-18 | 2012-01-18 | Use containing regenerating PC and the photocopier of regenerative PET halogen-free fire-proof resin composition or the exterior member of printer |
| CN201210016861.X | 2012-01-18 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14/302,633 Continuation US8865795B1 (en) | 2012-01-18 | 2014-06-12 | Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20130237644A1 true US20130237644A1 (en) | 2013-09-12 |
Family
ID=47598706
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US13/743,934 Abandoned US20130237644A1 (en) | 2012-01-18 | 2013-01-17 | Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate |
| US14/302,633 Active US8865795B1 (en) | 2012-01-18 | 2014-06-12 | Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US14/302,633 Active US8865795B1 (en) | 2012-01-18 | 2014-06-12 | Copier/printer exterior part using halogen-free flame-retardant resin composition including recycled polycarbonate and recycled polyethylene terephthalate |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US20130237644A1 (en) |
| EP (1) | EP2617767B1 (en) |
| JP (1) | JP6214873B2 (en) |
| CN (1) | CN103214808B (en) |
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| EP4578914A1 (en) * | 2023-12-26 | 2025-07-02 | SHPP Global Technologies B.V. | Flame retardant polycarbonate compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103214808B (en) | 2016-12-14 |
| US20140296383A1 (en) | 2014-10-02 |
| JP2013147651A (en) | 2013-08-01 |
| EP2617767A1 (en) | 2013-07-24 |
| CN103214808A (en) | 2013-07-24 |
| JP6214873B2 (en) | 2017-10-18 |
| US8865795B1 (en) | 2014-10-21 |
| EP2617767B1 (en) | 2015-09-16 |
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