US20040249069A1 - Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing - Google Patents
Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing Download PDFInfo
- Publication number
- US20040249069A1 US20040249069A1 US10/485,117 US48511704A US2004249069A1 US 20040249069 A1 US20040249069 A1 US 20040249069A1 US 48511704 A US48511704 A US 48511704A US 2004249069 A1 US2004249069 A1 US 2004249069A1
- Authority
- US
- United States
- Prior art keywords
- polymer
- parts
- rubber
- graft
- resin composition
- 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
- 239000011342 resin composition Substances 0.000 title claims abstract description 103
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 43
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 141
- 229920000642 polymer Polymers 0.000 claims abstract description 123
- 239000000203 mixture Substances 0.000 claims abstract description 100
- 239000000178 monomer Substances 0.000 claims abstract description 99
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 60
- 238000000151 deposition Methods 0.000 claims abstract description 50
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 125000002897 diene group Chemical group 0.000 claims abstract 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 62
- 229920001577 copolymer Polymers 0.000 claims description 58
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 56
- -1 polydimethylsiloxane Polymers 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 45
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 37
- 239000004417 polycarbonate Substances 0.000 claims description 33
- 229920000728 polyester Polymers 0.000 claims description 30
- 229920000515 polycarbonate Polymers 0.000 claims description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 6
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 5
- 238000001465 metallisation Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 48
- 239000011347 resin Substances 0.000 abstract description 48
- 238000003466 welding Methods 0.000 abstract description 32
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 10
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 10
- 229920000126 latex Polymers 0.000 description 82
- 239000004816 latex Substances 0.000 description 80
- 238000004519 manufacturing process Methods 0.000 description 70
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 68
- 238000006116 polymerization reaction Methods 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 48
- 238000000034 method Methods 0.000 description 47
- 229920001971 elastomer Polymers 0.000 description 41
- 239000005060 rubber Substances 0.000 description 39
- 239000007864 aqueous solution Substances 0.000 description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 36
- 150000002500 ions Chemical group 0.000 description 35
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 33
- 239000003995 emulsifying agent Substances 0.000 description 27
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 22
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 22
- 239000007787 solid Substances 0.000 description 21
- 238000003756 stirring Methods 0.000 description 21
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 19
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 16
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 16
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 16
- 238000010559 graft polymerization reaction Methods 0.000 description 16
- 125000005375 organosiloxane group Chemical group 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 229920005992 thermoplastic resin Polymers 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 13
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 238000005345 coagulation Methods 0.000 description 12
- 230000015271 coagulation Effects 0.000 description 12
- 230000000379 polymerizing effect Effects 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 11
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 10
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000003377 acid catalyst Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000001993 dienes Chemical group 0.000 description 8
- 239000003999 initiator Substances 0.000 description 8
- 238000010526 radical polymerization reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 5
- 239000001639 calcium acetate Substances 0.000 description 5
- 235000011092 calcium acetate Nutrition 0.000 description 5
- 229960005147 calcium acetate Drugs 0.000 description 5
- 239000000701 coagulant Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 5
- 229940048086 sodium pyrophosphate Drugs 0.000 description 5
- 238000004544 sputter deposition Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 5
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- VLZDYNDUVLBNLD-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCCOC(=O)C(C)=C VLZDYNDUVLBNLD-UHFFFAOYSA-N 0.000 description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000005037 alkyl phenyl group Chemical group 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 150000008360 acrylonitriles Chemical class 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 239000012994 photoredox catalyst Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 229920006027 ternary co-polymer Polymers 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000008051 alkyl sulfates Chemical class 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical group 0.000 description 2
- 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 2
- 238000005282 brightening Methods 0.000 description 2
- YIEXROAWVNRRMJ-UHFFFAOYSA-N buta-1,3-diene;butyl prop-2-enoate Chemical compound C=CC=C.CCCCOC(=O)C=C YIEXROAWVNRRMJ-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 108700004121 sarkosyl Proteins 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- LVUDMQWOFGGAFN-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione;prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1.O=C1C=CC(=O)N1C1=CC=CC=C1 LVUDMQWOFGGAFN-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- VMAWODUEPLAHOE-UHFFFAOYSA-N 2,4,6,8-tetrakis(ethenyl)-2,4,6,8-tetramethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C=C[Si]1(C)O[Si](C)(C=C)O[Si](C)(C=C)O[Si](C)(C=C)O1 VMAWODUEPLAHOE-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- IGRYVRNQZARURF-UHFFFAOYSA-N 2-(dimethoxymethylsilyl)ethyl 2-methylprop-2-enoate Chemical compound COC(OC)[SiH2]CCOC(=O)C(C)=C IGRYVRNQZARURF-UHFFFAOYSA-N 0.000 description 1
- BQQGVSONEPNPAB-UHFFFAOYSA-N 3-(diethoxymethylsilyl)propyl 2-methylprop-2-enoate Chemical compound CCOC(OCC)[SiH2]CCCOC(=O)C(C)=C BQQGVSONEPNPAB-UHFFFAOYSA-N 0.000 description 1
- LOOUJXUUGIUEBC-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propane-1-thiol Chemical compound COC(OC)[SiH2]CCCS LOOUJXUUGIUEBC-UHFFFAOYSA-N 0.000 description 1
- WUTSHINWYBIRDG-UHFFFAOYSA-N 3-[ethoxy(diethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](CC)(CC)CCCOC(=O)C(C)=C WUTSHINWYBIRDG-UHFFFAOYSA-N 0.000 description 1
- JBDMKOVTOUIKFI-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(C)CCCOC(=O)C(C)=C JBDMKOVTOUIKFI-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- AIDAPOBEZDTRDC-UHFFFAOYSA-N 4-(diethoxymethylsilyl)butyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCCCC[SiH2]C(OCC)OCC AIDAPOBEZDTRDC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-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
- UDKBLXVYLPCIAZ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)-3,6-di(propan-2-yl)phenyl]phenol Chemical compound C=1C=C(O)C=CC=1C=1C(C(C)C)=CC=C(C(C)C)C=1C1=CC=C(O)C=C1 UDKBLXVYLPCIAZ-UHFFFAOYSA-N 0.000 description 1
- RQTDWDATSAVLOR-UHFFFAOYSA-N 4-[3,5-bis(4-hydroxyphenyl)phenyl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC(C=2C=CC(O)=CC=2)=CC(C=2C=CC(O)=CC=2)=C1 RQTDWDATSAVLOR-UHFFFAOYSA-N 0.000 description 1
- CIEGINNQDIULCT-UHFFFAOYSA-N 4-[4,6-bis(4-hydroxyphenyl)-4,6-dimethylheptan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC(C)(C=1C=CC(O)=CC=1)CC(C)(C)C1=CC=C(O)C=C1 CIEGINNQDIULCT-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RVSIHAVHOXSBJR-UHFFFAOYSA-N C(=CC1=CC=CC=C1)C=CC#N.C1(=CC=CC=C1)N1C(C=CC1=O)=O Chemical compound C(=CC1=CC=CC=C1)C=CC#N.C1(=CC=CC=C1)N1C(C=CC1=O)=O RVSIHAVHOXSBJR-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- IUMSDRXLFWAGNT-UHFFFAOYSA-N Dodecamethylcyclohexasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 IUMSDRXLFWAGNT-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940010048 aluminum sulfate Drugs 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- YLTDNYQTDYMOBH-UHFFFAOYSA-N bis(prop-2-enyl) 2-hydroxybutanedioate Chemical compound C=CCOC(=O)C(O)CC(=O)OCC=C YLTDNYQTDYMOBH-UHFFFAOYSA-N 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CAKGQGACNVJODG-UHFFFAOYSA-N butyl prop-2-enoate;2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCOC(=O)C=C.CCCCC(CC)COC(=O)C(C)=C CAKGQGACNVJODG-UHFFFAOYSA-N 0.000 description 1
- HBTYDDRQLQDDLZ-UHFFFAOYSA-N butyl prop-2-enoate;2-ethylhexyl prop-2-enoate Chemical compound CCCCOC(=O)C=C.CCCCC(CC)COC(=O)C=C HBTYDDRQLQDDLZ-UHFFFAOYSA-N 0.000 description 1
- MCKACQKLXKGBAT-UHFFFAOYSA-N butyl prop-2-enoate;octadecyl prop-2-enoate Chemical compound CCCCOC(=O)C=C.CCCCCCCCCCCCCCCCCCOC(=O)C=C MCKACQKLXKGBAT-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000008121 dextrose Substances 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- LIYUFTTVSMBDTB-UHFFFAOYSA-N dimethoxymethyl-(4-ethenylphenyl)silane Chemical compound COC(OC)[SiH2]C1=CC=C(C=C)C=C1 LIYUFTTVSMBDTB-UHFFFAOYSA-N 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- XNCMOUSLNOHBKY-UHFFFAOYSA-H iron(3+);trisulfate;heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XNCMOUSLNOHBKY-UHFFFAOYSA-H 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- DEAKWVKQKRNPHF-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enenitrile;styrene Chemical compound C=CC#N.COC(=O)C(C)=C.C=CC1=CC=CC=C1 DEAKWVKQKRNPHF-UHFFFAOYSA-N 0.000 description 1
- ADFPJHOAARPYLP-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1 ADFPJHOAARPYLP-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical class C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229960002816 potassium chloride Drugs 0.000 description 1
- 229940096992 potassium oleate Drugs 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- FKWJAWVTUCWKFH-UHFFFAOYSA-L sodium formaldehyde sulfoxylate dihydrate Chemical compound O.O.[Na+].[Na+].O=C.[O-]S[O-] FKWJAWVTUCWKFH-UHFFFAOYSA-L 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L51/003—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 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08L51/04—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 grafted on to rubbers
-
- 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
- C08L51/08—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 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
- C08L51/085—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 grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to a so-called direct vapor-depositing resin composition capable of directly forming a layer made of a metal such as aluminum, chromium and the like by metallizing treatment such as a vacuum vapor depositing method, sputtering method and the like without imparting surface treatment and under coat, for obtaining a brightening-treated molded article, further, to a resin composition suitable for lamp housings and, a molded article and lamp housing using the same.
- Thermoplastic resin molded articles for automobile parts and various electric appliance housings are sometimes subjected to metallizing treatment such as formation of a metal layer of copper, chromium, nickel and the like on the surface of a molded article by plating surface treatment, and formation of a metal layer of aluminum, chromium and the like on the surface of a molded article by a vacuum vapor depositing method, sputtering method and the like, for enhancing design and other functions.
- JP-A Japanese Patent Application Laid-Open
- JP-A No. 2001-2869 discloses a thermoplastic resin composition excellent in direct vapor depositing property comprising a rubber-containing graft copolymer obtained by graft-polymerizing a vinyl-based monomer (styrene, acrylonitrile) to a rubber-like polymer having specific particle size distribution (polyorganosiloxane-based polymers, acrylate polymers and the like), and a hard copolymer obtained by copolymerizing an aromatic vinyl-based monomer, a vinyl cyanide-based monomer and optionally other copolymerizable unsaturated monomers.
- a rubber-containing graft copolymer obtained by graft-polymerizing a vinyl-based monomer (styrene, acrylonitrile) to a rubber-like polymer having specific particle size distribution (polyorganosiloxane-based polymers, acrylate polymers and the like)
- JP-A No. 2002-133916 discloses, as a lamp housing material for automobile lamp equipments, a rubber-reinforced styrene-based resin composed of a graft polymer obtained by polymerizing an aromatic vinyl-based monomer (styrene, ⁇ -methylstyrene and the like) and a vinyl cyanide monomer (acrylonitrile and the like) in the presence of a rubber-like polymer having specific particle size distribution (polybutadiene-based rubber, ethylene-propylene-based rubber, acrylic rubber, silicone-based rubber and the like), or composed of a copolymer obtained by polymerizing the above-mentioned graft polymer and the above-mentioned monomer.
- a rubber-reinforced styrene-based resin composed of a graft polymer obtained by polymerizing an aromatic vinyl-based monomer (styrene, ⁇ -methylstyrene and the like) and a vinyl cyanide mono
- Automobile tail lamps, stop lamps, head lamps and the like are generally constituted of a lens made of a transparent resin such as PMMA (polymethyl methacrylate) resins, PC (polycarbonate) resins and the like, and a housing supporting the lens. Since such an automobile lamp housing is often exposed to sunlight outdoors, materials excellent in weather resistance are desired, in recent years.
- a transparent resin such as PMMA (polymethyl methacrylate) resins, PC (polycarbonate) resins and the like
- a so-called hot plate welding method is becoming general, in which in connecting a lens made of a transparent resin and a housing, a heated hot plate is pushed for several seconds to an adhesion part at which both materials are connected to heat-melt the both materials, and the hot plate is quickly removed, connecting the both materials.
- a phenomenon sometimes occurs in which each part of the both materials adheres to a hot plate of high temperature and stringiness occurs in removing the hot plate, therefore, it is important that this stringiness is scarce in using these materials.
- JP-A No. 10-310676 discloses, a hot plate welding thermoplastic resin composition composed of 10 to 100 parts by weight of a graft polymer obtained by graft-polymerizing at least one monomer unit selected from the group consisting of a vinyl cyanide monomer, an aromatic monomer, a (meth)acrylate monomer and other vinyl monomers in the presence of at least one rubber-like polymer selected from the group consisting of cross-linked acrylic rubbers and polyorganosiloxane-based rubbers, and 0 to 90 parts by weight of a copolymer composed of an aromatic vinyl-based monomer unit, a vinyl cyanide monomer unit and other vinyl-based monomer units.
- JP-A No. 2000-336235 discloses, as a resin composition significantly improving stringiness in a hot plate welding method, an automobile lamp equipment lamp body resin prepared by compounding 3 to 30% by weight of a homopolymer of a methacrylate or a copolymer of monomer components containing a methacrylate as a main component in 97 to 70% by weight of a rubber-reinforced styrene-based resin.
- JP-A No. 2000-302824 discloses a thermoplastic resin composition containing a graft copolymer (A) having a rubber-like graft copolymer obtained by polymerizing 10 to 1000 parts by weight of (II) a monomer mixture composed of 50 to 100% by weight of a monomer unit composed of methyl methacrylate and/or styrene and 0 to 50% by weight of a monomer unit copolymerizable with the above-mentioned monomer unit, to 100 parts by weight of (I) a rubber-like copolymer obtained by polymerizing a monomer mixture containing an alkyl acrylate monomer unit and a 1,3-butadiene monomer unit, as a thermoplastic resin composition performing excellent welding with a PMMA resin, PC resin and the like by vibration welding, showing excellent appearance of melted portions occurring in vibration welding and manifesting a good vibration welding property, and a molded body made of this thermoplastic resin composition.
- the resin compositions excellent in a direct vapor deposition property disclosed in JP-A Nos. 2001-2869 and 2002-133916 are not necessarily sufficient for responding a recent high requirement level for brightness. Furthermore, in applications such as an automobile lamp housing and the like, it is necessary that a molded article additionally has high weather resistance level.
- brightness of higher level can be manifested, however, in this case, decrease in impact resistance and weather resistance is often remarkable, and it is difficult to simultaneously satisfy brightness by direct vapor deposition treatment, impact resistance and weather resistance. Also, a hot plate welding property is often not satisfactory.
- thermoplastic resin composition described in examples of JP-A No. 2000-302824, disclosed is gloss retention after an exposure time of 500 hours in an accelerated exposure weather resistance test by a sunshine weather meter, however, sufficient weather resistance is not obtained for exposure of further longer time and level recently required is not necessarily attained.
- the object of the present invention is to provide a direct vapor depositing resin composition giving beautiful bright appearance after direct vapor deposition, further, having high level impact resistance and weather resistance, and also excellent in a hot plate welding property with a transparent resin such as PMMA resins, PC resins and the like (showing little stringiness), and a molded article and a lamp housing obtained by using this resin composition.
- the present invention relates to a direct vapor depositing resin composition
- a direct vapor depositing resin composition comprising at least one selected from the group consisting of the following graft copolymers (A-I) and (A-II).
- the present invention relates to the above-mentioned direct vapor depositing resin composition
- a vinyl-based (co)polymer (B) having as a constituent unit at least one selected from the group consisting of aromatic alkenyl units, vinyl cyanide units and alkyl(meth)acrylates.
- the present invention relates to the above-mentioned direct vapor depositing resin composition comprising a polycarbonate and/or polyester (C).
- the present invention relates to a molded article obtained by molding the above-mentioned direct vapor depositing resin composition.
- the present invention relates to the above-mentioned molded article of which surface has been metallized by direct vapor deposition.
- the present invention relates to a lamp housing obtained by metallization by direct vapor deposition of the surface of a molded article obtained by molding the above-mentioned direct vapor depositing resin composition.
- the direct vapor depositing resin composition of the present invention comprises at least one selected from the group consisting of the above-mentioned graft copolymers (A-I) and (A-II). If necessary, the direct vapor depositing resin composition may further contain the above-mentioned vinyl-based (co)polymer (B), and, may contain a polycarbonate and/or polyester (C).
- the total content of the graft copolymers (A-I) and (A-II) is preferably from 5 to 100% by weight, more preferably from 5 to 95% by weight based on the total amount of the graft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer (B).
- the content of a vinyl-based (co)polymer (B) is preferably from 95 to 0% by weight, more preferably from 95 to 5% by weight based on the total amount of the graft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer (B).
- the content of the vinyl-based (co)polymer (B) is more preferably 10% by weight or more and more preferably 90% by weight or less based on the total amount of the graft copolymers (A-I) and (A-II) and a vinyl-based (co)polymer (B).
- the total content of the graft copolymers (A-I) and (A-II) is from 5 to 80% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C), the content of the vinyl-based (co)polymer (B) is from 75 to 0% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C), and the content of the polycarbonate and/or polyester (C) is from 95 to 20% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).
- a vinyl-based (co)polymer (B) when a vinyl-based (co)polymer (B) is used, its content is preferably 20% by weight or more, particularly 30% by weight or more and preferably 90% by weight or less, particularly 80% by weight or less based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).
- a polycarbonate and/or polyester (C) When a polycarbonate and/or polyester (C) is used, its content is preferably 20% by weight or more, particularly 30% by weight or more and preferably 90% by weight or less, particularly 80% by weight or less based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).
- thermoplastic resins described later may be compounded in an amount within the range in which various abilities intended in the present invention are not significantly disturbed.
- the direct vapor depositing resin composition of the present invention may contain the above-mentioned graft copolymer (A-I) or (A-II), and may also contain the above-mentioned graft copolymers (A-I) and (A-II) together.
- the graft copolymer (A-I) is not required to be used singly, and two or more copolymers may be used in admixture.
- the graft copolymer (A-II) is also not required to be used singly, and two or more copolymers may be used in admixture.
- the direct vapor depositing resin composition of the present invention may contain other graft copolymers than the graft copolymers (A-I) and (A-II), and it is preferable that the graft copolymers (A-I) and (A-II) are used in a ratio of 60% by weight or more based on all graft copolymers. It is further preferable that the graft copolymers (A-I) and (A-II) are used in a ratio of 100% by weight based on all graft copolymers.
- a molded article made of such a direct vapor depositing resin composition of the present invention can be subjected to surface metallizing treatment by which a metal layer of aluminum, chromium and the like is formed on the surface of a molded article by a vacuum vapor depositing or sputtering method, without effecting special pre-treatment such as formation of an under coat-treated layer and the like.
- a bright molded article obtained by this direct vapor depositing method shows a beautiful bright appearance without surface haze, since the surface smoothness of a molded article made of the direct vapor depositing resin composition of the present invention is excellent.
- the direct vapor depositing resin composition of the present invention is excellent both in impact resistance and weather resistance.
- a molded article made of the direct vapor depositing resin composition of the present invention can be bonded to a transparent resin such as a PC resin, PMMA resin and the like by the hot plate welding method. Additionally, a stringing phenomenon scarcely occurs in this procedure, the appearance of the bonded part is excellent, and its bonding strength is also sufficiently high.
- the direct vapor depositing resin composition of the present invention is suitable for, for example, lamp housings and the like, and automobile lamps excellent in brightness, appearance, weather resistance and impact resistance can be produced efficiently according to the present invention.
- the polyorganosiloxane constituting the graft copolymer (A-I) according to the present invention preferably contains silicon atoms having three or more siloxane bonds in an amount of 1 mol % or less (including 0 mol %) based on all silicon atoms in polydimethylsiloxane.
- this amount is 1 mol % or less, the finally resulted resin composition is excellent in impact resistance.
- This amount is further preferably 0.8 mol % or less since then the resulted resin composition is excellent both in impact resistance and brightness after direct vapor deposition.
- the method of controlling the amount of silicon atoms having three or more siloxane bonds is not particularly restricted, and as an example, it is preferable to decrease the ratio of silicon-based monomers used for forming a cross-linked structure such as ethyl orthosilicate, tetraethoxysilane and the like in producing a polyorganosiloxane, and it is more preferable to use no silicon-based monomers used for forming a cross-linked structure.
- organosiloxane containing a vinyl-polymerizable functional group it is preferable, in producing a polyorganosiloxane, to use an organosiloxane containing a vinyl-polymerizable functional group.
- the amount of organosiloxane units containing a vinyl polymerizable functional group in a polyorganosiloxane is preferably 0.3 mol % or more since then complexation of a polyorganosiloxane with (meth)acrylate rubber progresses sufficiently, a polyorganosiloxane scarcely bleeds out on the surface of the finally resulted resin composition molded article, and brightness after direct vapor deposition of a molded article and close adherence between a metal and a resin are excellent.
- the amount of organosiloxane units containing a vinyl-polymerizable functional group in a polyorganosiloxane is 0.5 mol % or more since then the finally obtained resin composition is excellent both in impact resistance and brightness after direct vapor deposition.
- the amount of organosiloxane units containing a vinyl-polymerizable functional group in a polyorganosiloxane is preferably 3 mol % or less since then the finally obtained resin composition is excellent in impact resistance. Further, the amount of organosiloxane units containing a vinyl-polymerizable functional group in a polyorganosiloxane is further preferably 2 mol % or less, particularly 1 mol % or less since then the finally obtained resin composition is excellent both in impact resistance and brightness after direct vapor deposition.
- the polyorganosiloxane particularly, it is preferable to use a polyorganosiloxane composed of 0.3 to 3 mol % of organosiloxane units containing a vinyl-polymerizable functional group and 97 to 99.7 mol % of a dimethylsiloxane unit in which the amount of silicon atoms having three or more siloxane bonds is 1 mol % or less (including 0 mol %) based on all silicon atoms in the polyorganosiloxane.
- dimethylsiloxane used in producing a polyorganosiloxane tri- or more-cyclic dimethylsiloxane-based cyclic bodies are listed, and tri to hepta-cyclic bodies are preferable. Specifically listed are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and the like. These are used alone or in combination of two or more.
- the organosiloxane containing a vinyl-polymerizable functional group which can be used in production of a polyorganosiloxane contains a vinyl-polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond.
- methacryloyloxysiloxane such as ⁇ -methacryloyloxyethyldimethoxymethylsilane, ⁇ -methacryloyloxypropyldimethoxymethylsilane, ⁇ -methacryloyloxypropylmethoxydimethylsilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropylethoxydiethylsilane, ⁇ -methacryloyloxypropyldiethoxymethylsilane, ⁇ -methacryloyloxybutyldiethoxymethylsilane and the like, vinyl siloxanes such as tetramethyltetravinylcyclotetrasiloxane and the like, p-vinylphenyldimethoxymethylsilane, further, mercaptosiloxanes such as ⁇ -mercaptopropyldimethoxymethylsilane,
- the size of a polyorganosiloxane is not particularly restricted, and the average particle size is preferably 600 nm or less, particularly 200 nm or less for the purpose of enhancing brightness after direct vapor deposition of the finally obtained resin composition.
- the method of producing a polyorganosiloxane is not particularly restricted, and the following method is mentioned as one example.
- an emulsifier and water are added and emulsified, to obtain latex.
- this latex is finely granulated by using a homo-mixer of finely granulating by shearing force generated by high speed rotation, a homogenizer of finely granulating by injection force generated by a high pressure generator, and the like.
- a high pressure emulsifying apparatus such as a homogenizer and the like is preferable since then the distribution of the particle size of the polyorganosiloxane latex is small.
- This latex after fine granulation is added in an acid aqueous solution containing an acid catalyst, and polymerized under high temperature. Termination of polymerization can be conducted by cooling the reaction solution, further, neutralizing the solution with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate and the like.
- an acid catalyst may be previously mixed with a siloxane mixture, emulsifier and water, or an acid aqueous solution of high temperature may be dropped at a constant speed into latex in which a siloxane mixture has been finely granulated.
- latex in which a siloxane mixture has been finely granulated is dropped at a constant speed into an acid aqueous solution of high temperature, since then the particle size of the resulted polyorganosiloxane can be controlled easily.
- the polymerization time is, when an acid catalyst is mixed and granulated with a siloxane mixture, emulsifier and water before polymerization, preferably 2 hours or longer, particularly 4 hours or longer.
- a siloxane mixture emulsifier and water before polymerization
- the polymerization temperature is preferably 50° C. or more, particularly 80° C. or more.
- the upper limit of the polymerization temperature is not particularly restricted, and usually about 95° C.
- emulsifiers such as sodium alkylbenzensulfonates, sodium polyoxyethylene alkyl phenyl ether sulfates and the like, and of them, sulfonic acid-based emulsifiers such as sodium alkylbenzenesulfonates, sodium laurylsulfonate and the like are particularly preferable. These emulsifiers may be used alone or in combination of two or more.
- the use amount of an emulsifier is preferably 0.05 parts by weight or more based on 100 parts by weight of a siloxane mixture since then dispersed conditions is usually stable and emulsified condition of fine particles can be kept, and preferably 5 parts by weight or less based on 100 parts by weight of a siloxane mixture since then the color of a molded article is scarcely influenced by the color of an emulsifier itself or by deterioration of a resin composition ascribable to it.
- the acid catalyst used in polymerization of a polyorganosiloxane are sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids, aliphatic substituted naphthalenesulfonic acids and the like, and mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and the like. These acid catalysts may be used alone or in combination of two or more. As the acid catalyst, aliphatic substituted benzenesulfonic acids are preferable and n-dodecylbenzenesulfonic acid is particularly preferable because of excellent action of stabilizing polyorganosiloxane latex.
- n-dodecylbenzenesulfonic acid When n-dodecylbenzenesulfonic acid is combined with a mineral acid such as sulfuric acid and the like, an influence exerted by the color of an emulsifier used in polyorganosiloxane latex on the color of a resin composition molded article can be suppressed to lower level.
- the addition amount thereof may be appropriately determined, and usually from about 0.1 to 20 parts by weight based on 100 parts by weight of a siloxane mixture.
- the (meth)acrylate-based polymer constituting the complex rubber-like polymer (G) used in the graft copolymer (A-I) is obtained by polymerizing an alkyl (meth)acrylate monomer, or a monomer mixture containing one or more alkyl(meth)acrylates.
- the (meth)acrylate-based polymer may contain other monomers than the alkyl (meth)acrylate monomer.
- alkyl(meth)acrylate monomer examples include, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate and the like.
- alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like
- alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate and the like.
- n-butyl acrylate is preferably used since then the resulted
- Polymerization can be conducted according to known methods. As described later, a graft crossing agent or cross-linking agent may be used.
- the method of producing a complex rubber-like polymer (G) used in the present invention is not particularly restricted, and there are listed a method in which separate latexes of a polyorganosiloxane and a (meth)acrylate-based polymer are hetero-aggregated or co-thickened, a method in which, in the presence of any one or more latexes, monomers (including also a mixture) forming other one or more polymers are polymerized and complexed, and other methods.
- graft crossing agent and cross-linking agent are, for example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and the like. These may be used alone or in combination of two or more.
- the addition amount thereof may be appropriately determined, and is preferably from about 0.3 to 6 parts by weight based on 100 parts by weight of (meth)acrylate monomers (including also a mixture) since then the resulted resin composition is excellent in impact resistance and brightness after direct vapor deposition.
- a monomer mixture constituted of these alkyl(meth) acrylates, and if necessary, a graft crossing agent and a cross-linking agent can be radical-polymerized in bulk, continuously or intermittently to a polyorganosiloxane in the form of latex, to obtain a polyorganosiloxane/(meth)acrylate-based complex rubber-like polymer (G).
- the content of a polyorganosiloxane in a complex rubber-like polymer (G) is 1% by weight or more based on the total amount of a polyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture) since then the resulted resin composition is excellent in impact resistance.
- the content of a polyorganosiloxane in a complex rubber-like polymer (G) is preferably 99% by weight or less, more preferably 90% by weight or less based on the total amount of a polyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture) since then the resulted resin composition is excellent in balance of impact resistance and brightness after direct vapor deposition.
- the amount of a polyorganosiloxane in a complex rubber-like polymer (G) is in this range, the resulted resin composition is excellent in impact resistance and brightness after direct vapor deposition.
- the amount of a polyorganosiloxane in a complex rubber-like polymer (G) is further preferably 2% by weight or more, particularly 3% by weight or more, and further preferably 50% by weight or less, particularly 10% by weight or less based on the total amount of a polyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture).
- the average particle size of a complex rubber-like polymer (G) is not particularly restricted, and preferably less than 400 nm, further preferably 300 nm or less since then the resulted resin composition is excellent in bright appearance after direct vapor deposition.
- the lower limit of the average particle size of a complex rubber-like polymer (G) is not particularly restricted, and usually about 30 nm.
- the ratio of rubber-like polymers having a particle size of 500 nm or more is 4% by weight or less (including 0% by weight), particularly 3% by weight or less, further 2% by weight or less based on 100% by weight of all rubber-like polymers including a complex rubber-like polymer (G) since then a molded article having a beautiful bright appearance is obtained.
- the graft copolymer (A-I) can be produced by emulsion-graft-polymerizing vinyl-based monomers, preferably, at least one monomer component selected from the group consisting of aromatic alkenyl compounds, alkyl (meth)acrylates and vinyl cyanide compounds to a complex rubber-like polymer (G) described above.
- styrene ⁇ -methylstyrene, vinyltoluene and the like are listed, for example, as the aromatic alkenyl compound.
- alkyl(meth)acrylate for example, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like are listed.
- vinyl cyanide compound for example, acrylonitrile, methacrylonitrile and the like are listed.
- a mixture of styrene and acrylonitrile is preferably used as the monomer component since then the resulted resin composition is excellent in impact resistance.
- the content of styrene in 100% by weight of this mixture is preferably 10% by weight or more, and preferably 90% by weight or less.
- the content of a complex rubber-like polymer (G) is 10% by weight or more and the content of a vinyl-based monomer is 90% by weight or less (in total: 100% by weight, the same in the followings) since then the finally resulted resin composition is excellent in impact resistance and also excellent in brightness after direct vapor deposition.
- the weight ratio of a complex rubber-like polymer (G) and a vinyl-based monomer used in emulsion-graft-polymerization it is preferable that the content of a complex rubber-like polymer (G) is 80% by weight or less and the content of a vinyl-based monomer is 20% by weight or more since then the finally resulted resin composition is excellent in impact resistance.
- the finally resulted resin composition is excellent in impact resistance, flowability and brightness after direct vapor deposition.
- the weight ratio of a complex rubber-like polymer (G) and a vinyl-based monomer used in emulsion-graft-polymerization it is preferable that the content of a complex rubber-like polymer (G) is 30% by weight or more and the content of a vinyl-based monomer is 70% by weight or less, and it is preferable that the content of a complex rubber-like polymer (G) is 70% by weight or less and the content of a vinyl-based monomer is 30% by weight or less.
- the finally resulted resin composition manifests excellent impact resistance and direct vapor deposition appearance excellent in brightness in good balance.
- the graft copolymer (A-I) can be produced by radical polymerization using an emulsifier.
- various chain transfer agents for controlling the graft ratio and the molecular weight of graft components for example, mercaptan-based compounds, terpene-based compounds, ⁇ -methylstyrene dimer and the like may be added.
- the polymerization conditions are not particularly restricted, and can be appropriately selected depending on necessity.
- radical polymerization initiator used in producing a graft copolymer (A-I) and a (meth)acrylate-based polymer in a complex rubber-like polymer (G) described above
- peroxides azo-based initiators, redox type initiators prepared by combining oxidizer and reducing agents, and the like
- redox type initiators are preferably used, and particularly, it is preferable to use redox type initiators combining ferrous sulfate . sodium pyrophosphate . glucose . hydroperoxide or ferrous sulfate . disodium ethylenediamine tetraacetate . rongalite . hydroperoxide.
- the emulsifier used in producing a graft copolymer (A-I) and a (meth)acrylate-based polymer in a complex rubber-like polymer (G) described above is not particularly restricted. Since an emulsifier used in production of a polyorganosiloxane is contained in a complex rubber-like polymer (G), this may be used itself, and if necessary, other emulsifiers may further be added.
- the emulsifier which can be used in this case, it is preferable to use various salts of carboxylic acids such as sodium sarcocinate, fatty potassium, fatty sodium, dipotassium alkenylsuccinate, rosin soap and the like, and anionic emulsifiers such as alkyl sulfates, sodium alkylbenzenesulfonates, sodium polyoxyethylene alkylphenyl ether sulfate and the like since then the stability of latex in emulsion-polymerization is excellent and polymerization ratio is enhanced. These are classified and used depending on the object. Further, it may also be permissible that the emulsifier used in preparation of a complex rubber-like polymer (G) is used as it is and emulsifiers are not additionally added in emulsion-graft-polymerization.
- carboxylic acids such as sodium sarcocinate, fatty potassium, fatty sodium, dipotassium alkenylsuccinate,
- the graft copolymer (A-II) used in the present invention is obtained by graft-polymerizing one or more monomers or a monomer mixture including an alkyl (meth)acrylate as an essential component to a rubber-like polymer (R) in which the content of diene units is 30% by weight or less (including 0% by weight) in 100% by weight of all rubber-like polymers contained in a resin composition.
- the graft copolymer (A-II) may be used singly or in combination of two or more, and can be selected optionally depending on its application.
- the rubber-like polymer (R) which can be used is not particularly restricted excepting the above-mentioned conditions, and exemplified are diene-based rubber such as polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl acrylate-butadiene rubber and the like, acrylic rubber such as butyl acrylate rubber, butadiene-butyl acrylate rubber, 2-ethylhexyl acrylate-butyl acrylate rubber, 2-ethylhexyl methacrylate-butyl acrylate rubber, stearyl acrylate-butyl acrylate rubber, dimethylsiloxane-butyl acrylate rubber, silicone/butyl acrylate complex rubber and the like, polyolefin-based rubber polymers such as ethylene-propylene rubber, ethylene-propylene-diene rubber and the like, silicone-based rubber polymers such as polydimethyl
- the content of diene units in 100% by weight of all rubber-like polymers is 30% by weight or less, preferably 10% by weight or less, further preferably less than 1% by weight since then the resulted resin composition is excellent in weather resistance.
- the rubber-like polymer (R) contains at least one monomer of alkyl acrylates having an alkyl group containing 2 to 8 carbon atoms, more preferably 4 to 8 carbon atoms such as methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, 2-ethylhexyl acrylate and the like, and it is preferable that the ratio of alkyl acrylate units having an alkyl group containing 2 to 8 carbon atoms in the rubber-like polymer (R) is from 70 to 90% by weight since then the resulted resin composition is excellent in weather resistance, brightness after direct vapor deposition and the appearance of a hot plate welding connected part.
- copolymerizable vinyl-based monomers other than the above-mentioned monomers can be introduced in an amount of 30% by weight or less.
- vinyl-based monomers are not particularly restricted, and examples thereof include aromatic vinyl-based monomers such as styrene, ⁇ -methylstyrene, vinyltoluene and the like, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, graft crossing agents and cross-linking agents such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and the like, and other monomers. These may be used alone or in combination of two or more.
- the graft components of the graft copolymer (A-II) are composed of one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component, or one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component, and other vinyl-based monomers copolymerizable with them.
- alkyl(meth)acrylate examples include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate, n-butyl(meth)acrylate, 2-ethylhexyl (meth)acrylate and the like. These may be used alone or in combination of two or more. Of them, it is preferable to use methyl methacrylate since then the resulted resin composition is excellent in balance of impact resistance and brightness after direct vapor deposition.
- copolymerizable other vinyl-based monomers are not particularly restricted, and the above-mentioned aromatic vinyl-based monomers, vinyl cyanide-based monomers and the like are listed.
- the content of an alkyl(meth)acrylate in 100% by weight of all graft components is preferably from 20 to 100% by weight, more preferably from 50 to 100% by weight, further preferably from 70 to 100% by weight, particularly preferably from 80 to 100% by weight since then the resulted resin composition is excellent in weather resistance, and brightness after direct vapor deposition.
- a graft copolymer (A-II) is not particularly restricted, and for example, a graft copolymer (A-II) can be produced by emulsion-graft-polymerizing one or more monomer components (one or more monomers or a monomer mixture) to the above-mentioned rubber-like polymer (R).
- the content of a rubber-like polymer (R) in 100% by weight of a graft copolymer (A-II) is preferably 10% or more, more preferably 30% or more, and preferably 90% by weigh or less, more preferably 80% by weight or less.
- the graft copolymer (A-II) can be produced by radical-polymerization using an emulsifier. Usually, a rubber-like polymer (R) is previously produced by emulsion-polymerization, and then one or more monomers or a monomer mixture as graft components are added to this rubber-like polymer latex, and they are graft-polymerized to obtain a graft copolymer (A-II). In monomer components, various chain transfer agents for controlling the graft ratio and the molecular weight of graft components, for example, mercaptan-based compounds, terpene-based compounds, ⁇ -methylstyrene dimer and the like may be added. The polymerization conditions are not particularly restricted, and can be appropriately selected depending on necessity.
- radical polymerization initiator used in producing a rubber-like polymer (R) and a graft copolymer (A-II) peroxides, azo-based initiators, redox type initiators prepared by combining oxidizer and reducing agents, and the like can be used.
- redox type initiators are preferably used, and particularly, it is preferable to use redox type initiators combining ferrous sulfate . sodium pyrophosphate . glucose . hydroperoxide or ferrous sulfate . disodium ethylenediamine tetraacetate . rongalite . hydroperoxide.
- the emulsifier used in producing a rubber-like polymer (R) and a graft copolymer (A-II) is not particularly restricted, it is preferable to use various salts of carboxylic acids such as sodium sarcocinate, fatty potassium, fatty sodium, dipotassium alkenylsuccinate, rosin soap and the like, and anionic emulsifiers such as alkyl sulfates, sodium alkylbenzenesulfonates, sodium polyoxyethylene alkylphenyl ether sulfate and the like since then the stability of latex in emulsion-polymerization is excellent and polymerization ratio is enhanced. These are classified and used depending on the object. Further, it may also be permissible that the emulsifier used in preparation of a rubber-like polymer (R) is used as it is and emulsifiers are not additionally added in emulsion-graft-polymerization.
- carboxylic acids such as sodium sarc
- the latex of graft copolymers (A) obtained by emulsion-graft-polymerization can be recovered as a graft copolymer (A) by, for example, a wet method in which it is added into hot water containing a dissolved coagulant to cause coagulation in the form of slurry, a spray dry method in which a graft copolymer (A) latex is sprayed into a heated atmosphere to recover a graft copolymer (A) semi-directly, and the other methods.
- inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and the like, and metal salts such as potassium chloride, calcium acetate, aluminum sulfate, alum and the like, can be used.
- the coagulant used is selected in a pair with an emulsifier used in polymerization.
- a graft copolymer (A) can be recovered using any coagulant, however, when an emulsifier showing stable emulsification power also in an acid region such as a sodium alkylbenzenesulfonate is contained, the above-mentioned inorganic acids are insufficient, and it is necessary to use a metal salt as a coagulant.
- a dried graft copolymer (A) can be obtained in the form of powder or granule. Further, in this procedure, it is also possible that which discharged from a squeezing dehydrator or extruder is carrier directly to an extruder or a molding machine for producing a resin composition, to give a molded article.
- the vinyl-based (co)polymer (B) which can be used in the resin composition of the present invention is a (co)polymer having as a constituent unit at least one selected from the group consisting of aromatic alkenyl units, vinyl cyanide units and alkyl(meth)acrylate units, namely, is a (co)polymer obtained by polymerizing monomers (also including a mixture) including any one or more of aromatic alkenyl compounds, vinyl cyanide compounds and alkyl(meth)acrylate compounds.
- the vinyl-based (co)polymer (B) By inclusion of the vinyl-based (co)polymer (B), other effects than the object of the present invention such as improvement in molding processability of the resulted resin composition, impartment of heat resistance, and the like can be obtained, and can be selected depending on its object.
- the vinyl-based (co)polymer (B) may be a copolymer obtained by polymerizing a monomer mixture containing monomers other than aromatic alkenyl compounds, vinyl cyanide compounds and alkyl(meth)acrylate compounds, and for example, it is also preferable that the vinyl-based (co)polymer (B) is a copolymer obtained by polymerizing a monomer mixture composed of an aromatic alkenyl compound, vinyl cyanide compound and N-substituted maleimide.
- aromatic alkenyl units vinyl cyanide units and alkyl(meth)acrylate units constituting them
- the same compounds as those used in the above-mentioned graft polymerization can be used.
- maleimide-based monomers As the other monomer components than these compounds, maleimide-based monomers, maleic anhydride and the like are listed.
- maleimide-based monomer for example, maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmelaimide, N-propylmaleimide, N-cyclohexylmaleimide and the like are listed.
- the vinyl-based (co)polymer (B) resins such as an acrylonitrile-styrene copolymer (SAN) resin, polymethyl methacrylate (PMMA) resin, styrene-methyl methacrylate copolymer (MS) resin, acrylonitrile- ⁇ methylstyrene copolymer ( ⁇ SAN) resin, styrene-acrylonitrile-N-phenylmaleimide ternary copolymer (SAM) resin, polystyrene resin, acrylonitrile-styrene-methyl methacrylate ternary copolymer and the like are specifically preferable.
- the vinyl-based (co)polymer (B) may be used alone or in combination of two or more.
- a vinyl-based (co)polymer (B) having any molecular weight can be used.
- the polycarbonate (C) which can be used in the resin composition of the present invention is composed of a dihydroxydiarylalkane, and may be branched optionally. By inclusion of the polycarbonate (C), the heat resistance and impact resistance of the resulted resin composition can be improved.
- the dihydroxyarylalkane may have an alkyl group, chlorine atom or bromine atom at the ortho position to a hydroxyl group.
- Preferable as the dihydroxyarylalkane are 4,4′-dihydroxy-2,2′-diphenylpropane (bisphenol A), tetramethyl bisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene and the like.
- polycarbonate (C) those having any molecular weight can be used.
- the polycarbonate (C) can be produced by a known method, and in general, produced by reacting a dihydroxy compound or a polyhydroxy compound with a phosgene or a diester of carbonic acid.
- a branched polycarbonate is produced by substituting a part of a dihydroxy compound, for example, 0.2 to 2 mol % of this with a polyhydroxy compound.
- a polyhydroxy compound there are listed 1,4-bis(4′,4,2-dihydroxytriphenylmethyl)-benzene, phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-heptene-2,4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tri(4-hydroxyphenyl)-benzene, 1,1,1-tri(4-hydroxyphenyl)-ethane, 2,2-bis[4,4′-(4,4′-dihydroxyphenyl)cyclohexyl]propane and the like.
- the polycarbonate (C) may be used alone or in combination of two or more.
- the polyester (C) which can be used in the resin composition of the present invention is mainly composed of a polyalkylene terephthalate, and preferably contains, in a ratio of 50% by weight or more, that composed of an aromatic dicarboxylic acid having 8 to 22 carbon atoms and an alkylene glycol or cycloalkylene glycol having 2 to 22 carbon atoms.
- the polyester (C) By inclusion of the polyester (C), the molding processability and chemical resistance of the resulted resin composition can be improved.
- the polyester (C) may also contain, if necessary, an aliphatic dicarboxylic acid, for example, adipic acid, sebacic acid and the like, as a constituent unit, in an amount preferably of 80% by weight or less. Also, the polyester (C) may contain a polyalkylene glycol such as polyethylene glycol and the like as a constituent unit.
- polyester (C) used polyethylene terephthalate, polytetramethylene terephthalate and the like are particularly preferable.
- polyester (C) those having any molecular weight can be used.
- the polyester (C) may be used alone or in combination of two or more.
- thermoplastic resins may be compounded in an amount within the range in which various abilities intended in the present invention are not significantly disturbed, if necessary.
- the other thermoplastic resin is not particularly restricted, and examples thereof include polyolefins such as polyvinyl chloride, polyethylene, polypropylene and the like, styrene-based elastomers such as styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS) and the like, various olefin-based elastomers, various polyester-based elastomers, polyacetal resins, modified polyphenylene ethers (modified PPE resins), ethylene-vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyallylate, liquid crystal polyester resins, polyamide resins (nylon) and the like, and ABS resins, ASA resins and styrene-acrylonitrile-silicone (SAS) resin and the like out of
- thermoplastic resins are preferably 80 parts by weight or less in 100 parts by weight of a resin composition.
- the resin composition of the present invention can be produced by mixing and dispersing a graft copolymer (A), if necessary, a vinyl-based (co)polymer (B), polycarbonate and/or polyester (C), other thermoplastic resin by a V shaped blender or Henschel mixer and the like, and melt kneading this mixture by using an extruder or a kneader such as a Banbury mixer, press kneader, roll and the like.
- a graft copolymer A
- B vinyl-based (co)polymer
- C polycarbonate and/or polyester
- other thermoplastic resin by a V shaped blender or Henschel mixer and the like, and melt kneading this mixture by using an extruder or a kneader such as a Banbury mixer, press kneader, roll and the like.
- the resulted direct vapor depositing resin composition of the present invention can be used itself, or if necessary, after compounding of additives such as dyes, pigments, heat stabilizers, weather resistant aids, reinforcing agents, fillers, flame retardants, flame retardant aids, foaming agents, lubricants, plasticizers, antistatic additives and the like, as a production raw material of a molded article.
- the resin composition can be made into the intended molded article by various molding methods such as an injection molding method, extrusion molding method, blow molding method, compression molding method, calender molding method, inflation molding method and the like.
- the molded article made of the resin composition of the present invention which has been primary-processed by the above-mentioned various molding methods can be subjected to surface metallizing treatment with aluminum, chromium and the like by a vacuum vapor deposition method or sputtering method, without special pre-treatment such as formation of an undercoat-treated layer and the like, as described above.
- This metallized bright surface may be left as it is, however, for protecting the surface from generation of flaw by dust and the like, it is also possible to effect top coat treatment of forming a coat made of a silicon-based material and the like by painting and the like.
- the direct vapor depositing resin composition of the present invention is, particularly, suitable for lamp housings.
- a brightening-treated lamp housing molded article obtained by metallizing by direct vapor deposition of the surface of a molded article obtained by molding the direct vapor depositing resin composition of the present invention is made into contact with a resin made of a PC resin, PMMA resin and the like by a method such as hot plate welding, vibration welding and the like.
- the molded article of the present invention is particularly suitable for hot plate welding since it is excellent in stringing property.
- polyorganosiloxane (L-1) latex was dried at 170° C. for 30 minutes, and the solid content was measured to find it was 17.7%.
- the average particle size of the polyorganosiloxane (L-1) in latex was 50 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more was about 0%.
- the content of organosiloxane units having a vinyl polymerizable functional group in polydimethylsiloxane was 0.65 mol %, and the content of silicon atoms having three or more siloxane bonds was 0 mol % based on all silicon atoms in polydimethylsiloxane.
- This pre-mixed organosiloxane latex was charged into a reactor equipped with a cooling tube, jacket heater and stirring apparatus, and the mixture was heated at 80° C. for 5 hours, then, cooled to about 20° C., and left as it was for 48 hours. Then, the reaction product was neutralized with a sodium hydroxide aqueous solution to pH 7, completing polymerization.
- polyorganosiloxane (L-2) latex was dried at 170° C. for 30 minutes, and the solid content was measured to find it was 36.5%.
- the average particle size of the polyorganosiloxane (L-2) in latex was 160 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more was 0.3%.
- the content of organosiloxane units having a vinyl polymerizable functional group in polydimethylsiloxane was 0.3 mol %, and the content of silicon atoms having three or more siloxane bonds was 1.5 mol % based on all silicon atoms in polydimethylsiloxane.
- polyorganosiloxane latex (L-1) produced in 8 parts Production Example 1 (solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, and they were mixed, then, to this was added a mixture composed of n-butyl acrylate 42 parts allyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.1 part t-butyl hydroperoxide 0.11 parts.
- L-1 solid content
- Emal NC-35 polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.
- the average particle size of the complex rubber-like polymer was 120 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more in 100% by weight of this complex rubber-like polymer (solid) was 0.1%. Further, the liquid temperature in the reactor lowered to 70° C., then, to this complex rubber latex was added an aqueous solution composed of rongalite 0.25 parts ion exchanged water 10 parts, then, as the first stage, a mixture of acrylonitrile 2.5 parts styrene 7.5 parts t-butyl hydroperoxide 0.05 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C.
- graft copolymer latex obtained by graft- polymerizing acrylonitrile and styrene to a complex rubber-like polymer composed of a polyorganosiloxane (L-1) and butyl acrylate rubber.
- polyorganosiloxane latex (L-1) produced in 2 parts Production Example 1 (solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, and they were mixed, then, to this was added a mixture composed of n-butyl acrylate 48 parts allyl methacrylate 1.08 parts 1,3-butylene glycol dimethacrylate 0.36 parts t-butyl hydroperoxide 0.11 parts.
- L-1 solid content
- Emal NC-35 polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.
- the average particle size of the complex rubber-like polymer was 145 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more in 100% by weight of this complex rubber-like polymer (solid) was 0.3%.
- Graft polymerization was conducted in the same manner as in Production Example 4 excepting use of the resulted complex rubber, giving graft copolymer latex obtained by graft-polymerizing acrylonitrile and styrene to a complex rubber-like polymer composed of a polyorganosiloxane (L-1) and n-butyl acrylate rubber.
- polyorganosiloxane latex (L-2) produced in 30 parts Production Example 2 (solid content) ion exchanged water (including water in (L-2)) 295 parts, and the reactor was purged with nitrogen, then, the reaction mixture was heated to 50° C., and to this was added a mixture composed of n-butyl acrylate 37.5 parts allyl methacrylate 2.5 parts t-butyl hydroperoxide 0.3 parts, and the mixture was stirred for 30 minutes. Then, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.0003 parts disodium ethylenediamine tetraacetate 0.001 part rongalite 0.17 parts ion exchanged water 5 parts
- the average particle size of the complex rubber-like polymer was 190 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more in 100% by weight of this complex rubber-like polymer (solid) was 3%.
- this graft copolymer latex was added into a 12% calcium chloride aqueous solution of the same amount (liquid temperature: 60° C.) while stirring, then, a temperature of 80° C. was kept for 5 minutes, further, a temperature of 95° C. was kept for 5 minutes, to cause coagulation. The precipitate was separated, washed, and dehydrated, then, dried at 85° C. for 24 hours, to obtain a polyorganosiloxane/acrylate complex rubber-like graft copolymer (A-I-4).
- polybutadiene latex (average particle size: 50 parts 120 nm, ratio of particles having particle size of 500 nm or more: 0.2%) (solid content) at room temperature, and ion exchanged water (including water contained 140 parts in rubber-like polymer latex) glucose 0.6 parts anhydrous sodium pyrophosphate 0.01 part ferrous sulfate hepta-hydrate 0.005 parts sodium hydroxide 0.1 part were added, the reactor was purged with nitrogen while the reaction mixture was stirred, then, the reaction mixture was heated to 50° C.
- antioxidant (Antage W-400, manufactured by 1 part, Kawaguchi Kagaku Kogyo K.K.) and the latex was added into a 1.2% sulfuric acid aqueous solution (liquid temperature: 70° C.) of the same amount as this graft copolymer latex to cause coagulation, further, the temperature was raised to 90° C. and kept for 5 minutes, then, the product was dehydrated, washed and dried to obtain a diene-based graft copolymer (a-I-6) in the form of opalescent powder.
- the average particle size of the rubber-like polymer was 110 nm, and the ratio of particles having a particle size of 500 nm or more was about 0%.
- dipotassium alkenylsuccinate 0.3 parts (Latemul ASK manufactured by Kao Corp., as substantial amount, the same in the followings) ion exchanged water (including water in thickened 175 parts, butadiene-based polymer latex) and to this was added a mixture composed of n-butyl acrylate 40 parts, allyl methacrylate 0.16 parts, 1,3-butylene glycol dimethacrylate 0.08 parts, t-butyl hydroperoxide 0.1 part while stirring. The atmosphere was purged with nitrogen by passing a nitrogen flow through this reactor, the inner temperature was raised to 60° C.
- the average particle size of this complex rubber-based rubber-like polymer latex was 300 nm, and the ratio of particles having a particle size of 500 nm or more was 51%. Then, an aqueous solution composed of rongalite 0.15 parts dipotassium alkenylsuccinate 0.65 parts ion exchanged water 10 parts was added, then, mixed liquid of acrylonitrile 6.3 parts styrene 18.7 parts t-butyl hydroperoxide 0.11 parts was dropped over 1 hour, to cause polymerization.
- the above-mentioned polymer latex was added, while stirring, into a 0.6% sulfuric acid aqueous solution heated to 45° C. of an amount 1.2 fold of the whole latex, to coagulate a polymer. Then, the liquid temperature was raised to 65° C. and kept for 5 minutes, then, the liquid temperature was raised to 90° C. Then, the precipitate was separated, then, the recovered substance was added into water of 10-fold amount, then, stirred for 10 minutes, to effect washing treatment. This dispersion was dehydrated in a centrifugal dehydrator, further, dried at 80° C. for 16 hours, to obtain a graft copolymer (a-I-8).
- An acrylic resin (B-1) composed of 99 parts of methyl methacrylate and 1 part of methyl acrylate and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.25 dl/g was produced by known suspension polymerization.
- An acrylonitrile-styrene copolymer (B-2) composed of 29 parts of acrylonitrile and 71 parts of styrene and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.60 dl/g was produced by known suspension polymerization.
- An acrylonitrile-styrene-N-phenylmaleimide ternary copolymer (B-3) composed of 19 parts of acrylonitrile, 53 parts of styrene and 28 parts of N-phenylmaleimide and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.65 dl/g was produced by known continuous solution polymerization.
- An acrylonitrile-amethylstyrene copolymer (B-4) composed of 25 parts of acrylonitrile and 75 parts of a methylstyrene and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.50 dl/g was produced by known continuous solution polymerization.
- TEX-30 manufactured by N
- a white-colored plate of 100 mm ⁇ 100 mm ⁇ 3 mm was treated for 1000 hours by Sunshine-weather-meter (manufactured by Suga Shikenki K.K.) at a black panel temperature of 63° C. and a cycle condition of 60 minutes (raining: 12 minutes).
- the weather resistance was evaluated by the degree of discoloration (AE) measured by a color difference meter in this case.
- a plate of 100 mm ⁇ 100 mm ⁇ 3 mm was molded as a sample using an injection molding machine manufactured by Toshiba Machine Co., Ltd. “IS80FP” under conditions of a cylinder set temperature of 230° C., a mold temperature of 70° C. and an injection speed of 99%. Then, by a vacuum vapor deposition method, an aluminum vapor deposited film having a film thickness of about 50 nm was formed at a degree of vacuum of 1 ⁇ 10 ⁇ 6 Torr, an electric current value of 400 mA and a film formation speed of 1.5 mm/s. On this aluminum vapor deposited film, a top coat layer of SiO 2 was vapor-deposited.
- a hot plate processed with a fluorine resin was heated at a surface temperature of 300° C., a test sheet (30 mm ⁇ 100 mm ⁇ 3 mm) was allowed to contact with this hot plate for 30 seconds, then, the test sheet was lifted vertically, and the stringing length in this operation was measured, and the hot plate welding property was evaluated.
- the stringing length is less than 1 mm, the evaluation was ⁇ , when 1 mm or more and less than 5 mm, the evaluation was ⁇ , and when 5 mm or more, the evaluation was X.
- the direct vapor depositing resin compositions of the present invention in Examples 1 to 14 had high Izod impact strength and excellent weather resistance, and showed excellent brightness revealing low diffusion reflectance after direct vapor deposition. Further, the stringing length in hot plate welding was short, and the hot plate welding property was also excellent.
- the resin compositions in Comparative Examples 1 to 5 were inferior in any one or more of the Izod impact resistance, weather resistance, and brightness after direct vapor deposition.
- liquid temperature in the reactor lowered to 70° C., then, to this was added an aqueous solution composed of rongalite 0.25 parts ion exchanged water 10 parts, then, as the first stage, a mixture of methyl methacrylate 9.5 parts methyl acrylate 0.5 parts t-butyl hydroperoxide 0.05 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C.
- graft copolymer latex obtained by graft- polymerizing methyl methacrylate and methyl acrylate to a complex rubber-like polymer composed of a polyorganosiloxane and butyl acrylate rubber.
- This latex was coagulated and recovered in the same manner as for the graft copolymer (A-II-1) in Production Example 16, to obtain a graft copolymer (A-II-3) which is a white powder.
- polyorganosiloxane latex (L-3) (solid content) 8 parts Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, and these were mixed, then, a mixture composed of n-butyl acrylate 42 parts allyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.1 part t-butyl hydroperoxide 0.11 parts was added.
- L-3 solid content 8 parts
- Emal NC-35 polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.
- ion exchanged water 148.5 parts
- liquid temperature in the reactor lowered to 70° C., then, to this was added an aqueous solution composed of rongalite 0.25 parts ion exchanged water 10 parts, then, as the first stage, a mixture of methyl methacrylate 9.5 parts methyl acrylate 0.5 parts t-butyl hydroperoxide 0.05 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C.
- graft copolymer latex obtained by graft- polymerizing methyl methacrylate and methyl acrylate to a complex rubber-like polymer composed of a polyorganosiloxane and butyl acrylate rubber.
- polybutadiene latex (average particle size: 50 parts 290 nm) (solid content) at room temperature, and to this was added ion exchanged water (including water contained 140 parts in rubber-like polymer latex) glucose 0.6 parts anhydrous sodium pyrophosphate 0.01 part ferrous sulfate hepta-hydrate 0.005 parts sodium hydroxide 0.1 part and the atmosphere was purged with nitrogen while the reaction mixture was stirred, then the reaction mixture was raised to 50° C., into this was dropped a mixture composed of acrylonitrile 15 parts styrene 35 parts t-dodecylmercaptan 0.5 parts cumene hydroperoxide 0.3 parts over 180 minutes, and controlled so that the inner temperature was not over 65° C.
- Polymerization was conducted in the same manner as in Production Example 17 excepting that methyl methacrylate and methyl acrylate used in the first stage were changed to 2.5 parts of acrylonitrile and 7.5 parts of styrene, and methyl methacrylate and methyl acrylate used in the second stage were changed to 10 parts of acrylonitrile and 30 parts of styrene, obtaining graft copolymer latex obtained by graft-polymerizing acrylonitrile and styrene to a complex rubber-like polymer composed of a polyorganosiloxane and butyl acrylate rubber.
- graft copolymer latex To the resulted graft copolymer latex was added 0.4 parts of styrenated phenol, 0.3 parts of dilauryl thiopropionate and 0.4 parts of triphenyl phosphite, then, a 0.25% dilute sulfuric acid aqueous solution heated to 50° C. of an amount 2-fold of the graft latex was added to precipitate a graft copolymer, further, thermally treated at 90° C. for 5 minutes, then, washed with water, and dehydration thereof was repeated several times, and finally dried to obtain a graft copolymer (a-II-7) which is a white powder.
- Polymerization was conducted in the same manner as in Production Example 16 excepting that 36 parts of methyl methacrylate and 2 parts of methyl acrylate used in graft polymerization was changed to 10 parts of acrylonitrile and 28 parts of styrene, obtaining graft copolymer latex obtained by graft-polymerizing acrylonitrile and styrene to butyl acrylate rubber.
- the resin compositions of the present invention in Examples 15 to 27 had excellent weather resistance, and showed excellent brightness revealing low diffusion reflectance after direct vapor deposition. Further, the stringing length in hot plate welding was short, and the hot plate welding property was also excellent.
- the resin compositions in Comparative Examples 6 to 11 were inferior in any one or more of the weather resistance, brightness after direct vapor deposition and hot plate welding property.
- the ratio of methyl methacrylate in the grafted part composition (100% by weight) of a graft copolymer contained in the resin composition is preferably from 70 to 100% by weight.
- a direct vapor depositing resin composition capable of providing a beautiful bright appearance after direct vapor deposition of a metal, further, having high level mechanical strengths such as impact strength and the like, and weather resistance, and also excellent in hot plate welding property with a transparent resin such as PMMA resins, polycarbonate resins and the like, and a molded article obtained by using this resin composition, can be provided.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Non-Portable Lighting Devices Or Systems Thereof (AREA)
Abstract
The direct vapor depositing resin composition of the present invention comprises at least one selected from the group consisting of (A-I): a graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture to a complex rubber-like polymer (G) composed of a polyorganosiloxane and a (meth)acrylate-based polymer and (A-II): a graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component to a rubber-like polymer (R) in which the content of diene units is 30% by weight or less in 100% by weight of the whole rubber-like polymer. The direct vapor depositing resin composition of the present invention can provide a beautiful bright appearance after direct vapor deposition of a metal, further, has high level mechanical strengths such as impact strength and the like, and weather resistance, and is also excellent in hot plate welding property with a transparent resin such as PMMA resins, PC resins and the like.
Description
- The present invention relates to a so-called direct vapor-depositing resin composition capable of directly forming a layer made of a metal such as aluminum, chromium and the like by metallizing treatment such as a vacuum vapor depositing method, sputtering method and the like without imparting surface treatment and under coat, for obtaining a brightening-treated molded article, further, to a resin composition suitable for lamp housings and, a molded article and lamp housing using the same.
- Thermoplastic resin molded articles for automobile parts and various electric appliance housings are sometimes subjected to metallizing treatment such as formation of a metal layer of copper, chromium, nickel and the like on the surface of a molded article by plating surface treatment, and formation of a metal layer of aluminum, chromium and the like on the surface of a molded article by a vacuum vapor depositing method, sputtering method and the like, for enhancing design and other functions.
- Conventionally, in performing surface metallizing treatment by a vacuum vapor depositing method, sputtering method and the like on such a resin molded article, it is necessary to form an undercoat-treated layer by painting and plasma polymerization treatment, then, to form a metal layer (thickness: decades to several hundred nm) by a vacuum vapor depositing method and the like, for deleting irregularity on the surface of a molded article to obtain smoothness. Usually, thereafter, a top coat layer made of a silicon-based material and the like is formed for the purpose of protecting the metal layer. Thus, the metallizing treatment of a thermoplastic resin molded article requires complicated many processes and special apparatuses and expensive treating agents. However, there is conducted, recently, a so-called “direct vapor depositing method” in which a pre-treatment process of forming an undercoat-treated layer is abbreviated.
- However, the design of a bright molded article obtained by this “direct vapor depositing method” varies significantly depending on the kind of a resin material and the surface condition of a resin molded article. In the direct vapor depositing method, particularly, obtaining beautiful bright appearance without surface hazing is one of important subjects.
- For such a field, for example, Japanese Patent Application Laid-Open (JP-A) No. 2001-2869 discloses a thermoplastic resin composition excellent in direct vapor depositing property comprising a rubber-containing graft copolymer obtained by graft-polymerizing a vinyl-based monomer (styrene, acrylonitrile) to a rubber-like polymer having specific particle size distribution (polyorganosiloxane-based polymers, acrylate polymers and the like), and a hard copolymer obtained by copolymerizing an aromatic vinyl-based monomer, a vinyl cyanide-based monomer and optionally other copolymerizable unsaturated monomers.
- Also, JP-A No. 2002-133916 discloses, as a lamp housing material for automobile lamp equipments, a rubber-reinforced styrene-based resin composed of a graft polymer obtained by polymerizing an aromatic vinyl-based monomer (styrene, α-methylstyrene and the like) and a vinyl cyanide monomer (acrylonitrile and the like) in the presence of a rubber-like polymer having specific particle size distribution (polybutadiene-based rubber, ethylene-propylene-based rubber, acrylic rubber, silicone-based rubber and the like), or composed of a copolymer obtained by polymerizing the above-mentioned graft polymer and the above-mentioned monomer.
- Automobile tail lamps, stop lamps, head lamps and the like are generally constituted of a lens made of a transparent resin such as PMMA (polymethyl methacrylate) resins, PC (polycarbonate) resins and the like, and a housing supporting the lens. Since such an automobile lamp housing is often exposed to sunlight outdoors, materials excellent in weather resistance are desired, in recent years.
- Further, a so-called hot plate welding method is becoming general, in which in connecting a lens made of a transparent resin and a housing, a heated hot plate is pushed for several seconds to an adhesion part at which both materials are connected to heat-melt the both materials, and the hot plate is quickly removed, connecting the both materials. In the hot plate welding method, a phenomenon sometimes occurs in which each part of the both materials adheres to a hot plate of high temperature and stringiness occurs in removing the hot plate, therefore, it is important that this stringiness is scarce in using these materials.
- As a material in such a field, for example, JP-A No. 10-310676 discloses, a hot plate welding thermoplastic resin composition composed of 10 to 100 parts by weight of a graft polymer obtained by graft-polymerizing at least one monomer unit selected from the group consisting of a vinyl cyanide monomer, an aromatic monomer, a (meth)acrylate monomer and other vinyl monomers in the presence of at least one rubber-like polymer selected from the group consisting of cross-linked acrylic rubbers and polyorganosiloxane-based rubbers, and 0 to 90 parts by weight of a copolymer composed of an aromatic vinyl-based monomer unit, a vinyl cyanide monomer unit and other vinyl-based monomer units.
- JP-A No. 2000-336235 discloses, as a resin composition significantly improving stringiness in a hot plate welding method, an automobile lamp equipment lamp body resin prepared by compounding 3 to 30% by weight of a homopolymer of a methacrylate or a copolymer of monomer components containing a methacrylate as a main component in 97 to 70% by weight of a rubber-reinforced styrene-based resin.
- Further, JP-A No. 2000-302824 discloses a thermoplastic resin composition containing a graft copolymer (A) having a rubber-like graft copolymer obtained by polymerizing 10 to 1000 parts by weight of (II) a monomer mixture composed of 50 to 100% by weight of a monomer unit composed of methyl methacrylate and/or styrene and 0 to 50% by weight of a monomer unit copolymerizable with the above-mentioned monomer unit, to 100 parts by weight of (I) a rubber-like copolymer obtained by polymerizing a monomer mixture containing an alkyl acrylate monomer unit and a 1,3-butadiene monomer unit, as a thermoplastic resin composition performing excellent welding with a PMMA resin, PC resin and the like by vibration welding, showing excellent appearance of melted portions occurring in vibration welding and manifesting a good vibration welding property, and a molded body made of this thermoplastic resin composition.
- However, the resin compositions excellent in a direct vapor deposition property disclosed in JP-A Nos. 2001-2869 and 2002-133916 are not necessarily sufficient for responding a recent high requirement level for brightness. Furthermore, in applications such as an automobile lamp housing and the like, it is necessary that a molded article additionally has high weather resistance level. By further reducing the amount of the rubber component having large particle size specifically suggested in JP-A No. 2001-2869, brightness of higher level can be manifested, however, in this case, decrease in impact resistance and weather resistance is often remarkable, and it is difficult to simultaneously satisfy brightness by direct vapor deposition treatment, impact resistance and weather resistance. Also, a hot plate welding property is often not satisfactory.
- On the other hand, in the case of formation of a layer made of metal such as aluminum, chromium and the like by a direct vapor deposition method, on the resin compositions disclosed in examples of JP-A Nos. 10-310676 and 2000-336235, sufficient brightness is not necessarily obtained and, level recently required is not attained in some cases.
- Regarding the thermoplastic resin composition described in examples of JP-A No. 2000-302824, disclosed is gloss retention after an exposure time of 500 hours in an accelerated exposure weather resistance test by a sunshine weather meter, however, sufficient weather resistance is not obtained for exposure of further longer time and level recently required is not necessarily attained.
- The object of the present invention is to provide a direct vapor depositing resin composition giving beautiful bright appearance after direct vapor deposition, further, having high level impact resistance and weather resistance, and also excellent in a hot plate welding property with a transparent resin such as PMMA resins, PC resins and the like (showing little stringiness), and a molded article and a lamp housing obtained by using this resin composition.
- The present invention relates to a direct vapor depositing resin composition comprising at least one selected from the group consisting of the following graft copolymers (A-I) and (A-II).
- (A-I): A graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture to a complex rubber-like polymer (G) composed of a polyorganosiloxane and a (meth)acrylate-based polymer.
- (A-II): A graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component to a rubber-like polymer (R) in which the content of diene units is 30% by weight or less (including 0% by weight) in 100% by weight of the whole rubber-like polymer.
- Further, the present invention relates to the above-mentioned direct vapor depositing resin composition comprising a vinyl-based (co)polymer (B) having as a constituent unit at least one selected from the group consisting of aromatic alkenyl units, vinyl cyanide units and alkyl(meth)acrylates.
- Furthermore, the present invention relates to the above-mentioned direct vapor depositing resin composition comprising a polycarbonate and/or polyester (C).
- Still further, the present invention relates to a molded article obtained by molding the above-mentioned direct vapor depositing resin composition.
- Even further, the present invention relates to the above-mentioned molded article of which surface has been metallized by direct vapor deposition.
- Even still further, the present invention relates to a lamp housing obtained by metallization by direct vapor deposition of the surface of a molded article obtained by molding the above-mentioned direct vapor depositing resin composition.
- The direct vapor depositing resin composition of the present invention comprises at least one selected from the group consisting of the above-mentioned graft copolymers (A-I) and (A-II). If necessary, the direct vapor depositing resin composition may further contain the above-mentioned vinyl-based (co)polymer (B), and, may contain a polycarbonate and/or polyester (C).
- In the direct vapor depositing resin composition of the present invention, particularly when a polycarbonate and/or polyester (C) is not contained, the total content of the graft copolymers (A-I) and (A-II) is preferably from 5 to 100% by weight, more preferably from 5 to 95% by weight based on the total amount of the graft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer (B). Namely, the content of a vinyl-based (co)polymer (B) is preferably from 95 to 0% by weight, more preferably from 95 to 5% by weight based on the total amount of the graft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer (B). The content of the vinyl-based (co)polymer (B) is more preferably 10% by weight or more and more preferably 90% by weight or less based on the total amount of the graft copolymers (A-I) and (A-II) and a vinyl-based (co)polymer (B).
- In the direct vapor depositing resin composition of the present invention, it is preferable that the total content of the graft copolymers (A-I) and (A-II) is from 5 to 80% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C), the content of the vinyl-based (co)polymer (B) is from 75 to 0% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C), and the content of the polycarbonate and/or polyester (C) is from 95 to 20% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).
- Particularly, when a vinyl-based (co)polymer (B) is used, its content is preferably 20% by weight or more, particularly 30% by weight or more and preferably 90% by weight or less, particularly 80% by weight or less based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).
- When a polycarbonate and/or polyester (C) is used, its content is preferably 20% by weight or more, particularly 30% by weight or more and preferably 90% by weight or less, particularly 80% by weight or less based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).
- By controlling the ratio of a vinyl-based (co)polymer (B) in a resin composition within the above-mentioned range, the rigidity and molding processability of the resulting resin composition are improved. By controlling the ratio of a polycarbonate and/or polyester (C) in a resin composition within the above-mentioned range, objects of compounding such as heat resistance, impact resistance, chemical resistance and the like and the object of the present invention can be attained simultaneously.
- In the direct vapor depositing resin composition of the present invention, other thermoplastic resins described later may be compounded in an amount within the range in which various abilities intended in the present invention are not significantly disturbed.
- The direct vapor depositing resin composition of the present invention may contain the above-mentioned graft copolymer (A-I) or (A-II), and may also contain the above-mentioned graft copolymers (A-I) and (A-II) together. The graft copolymer (A-I) is not required to be used singly, and two or more copolymers may be used in admixture. The graft copolymer (A-II) is also not required to be used singly, and two or more copolymers may be used in admixture.
- The direct vapor depositing resin composition of the present invention may contain other graft copolymers than the graft copolymers (A-I) and (A-II), and it is preferable that the graft copolymers (A-I) and (A-II) are used in a ratio of 60% by weight or more based on all graft copolymers. It is further preferable that the graft copolymers (A-I) and (A-II) are used in a ratio of 100% by weight based on all graft copolymers.
- A molded article made of such a direct vapor depositing resin composition of the present invention can be subjected to surface metallizing treatment by which a metal layer of aluminum, chromium and the like is formed on the surface of a molded article by a vacuum vapor depositing or sputtering method, without effecting special pre-treatment such as formation of an under coat-treated layer and the like. A bright molded article obtained by this direct vapor depositing method shows a beautiful bright appearance without surface haze, since the surface smoothness of a molded article made of the direct vapor depositing resin composition of the present invention is excellent.
- The direct vapor depositing resin composition of the present invention is excellent both in impact resistance and weather resistance.
- Further, a molded article made of the direct vapor depositing resin composition of the present invention can be bonded to a transparent resin such as a PC resin, PMMA resin and the like by the hot plate welding method. Additionally, a stringing phenomenon scarcely occurs in this procedure, the appearance of the bonded part is excellent, and its bonding strength is also sufficiently high.
- Therefore, the direct vapor depositing resin composition of the present invention is suitable for, for example, lamp housings and the like, and automobile lamps excellent in brightness, appearance, weather resistance and impact resistance can be produced efficiently according to the present invention.
- The present invention will be described in detail below.
- The polyorganosiloxane constituting the graft copolymer (A-I) according to the present invention preferably contains silicon atoms having three or more siloxane bonds in an amount of 1 mol % or less (including 0 mol %) based on all silicon atoms in polydimethylsiloxane. When this amount is 1 mol % or less, the finally resulted resin composition is excellent in impact resistance. This amount is further preferably 0.8 mol % or less since then the resulted resin composition is excellent both in impact resistance and brightness after direct vapor deposition.
- The method of controlling the amount of silicon atoms having three or more siloxane bonds is not particularly restricted, and as an example, it is preferable to decrease the ratio of silicon-based monomers used for forming a cross-linked structure such as ethyl orthosilicate, tetraethoxysilane and the like in producing a polyorganosiloxane, and it is more preferable to use no silicon-based monomers used for forming a cross-linked structure.
- Further, it is preferable, in producing a polyorganosiloxane, to use an organosiloxane containing a vinyl-polymerizable functional group. The amount of organosiloxane units containing a vinyl polymerizable functional group in a polyorganosiloxane is preferably 0.3 mol % or more since then complexation of a polyorganosiloxane with (meth)acrylate rubber progresses sufficiently, a polyorganosiloxane scarcely bleeds out on the surface of the finally resulted resin composition molded article, and brightness after direct vapor deposition of a molded article and close adherence between a metal and a resin are excellent. It is further preferable that the amount of organosiloxane units containing a vinyl-polymerizable functional group in a polyorganosiloxane is 0.5 mol % or more since then the finally obtained resin composition is excellent both in impact resistance and brightness after direct vapor deposition.
- The amount of organosiloxane units containing a vinyl-polymerizable functional group in a polyorganosiloxane is preferably 3 mol % or less since then the finally obtained resin composition is excellent in impact resistance. Further, the amount of organosiloxane units containing a vinyl-polymerizable functional group in a polyorganosiloxane is further preferably 2 mol % or less, particularly 1 mol % or less since then the finally obtained resin composition is excellent both in impact resistance and brightness after direct vapor deposition.
- As the polyorganosiloxane, particularly, it is preferable to use a polyorganosiloxane composed of 0.3 to 3 mol % of organosiloxane units containing a vinyl-polymerizable functional group and 97 to 99.7 mol % of a dimethylsiloxane unit in which the amount of silicon atoms having three or more siloxane bonds is 1 mol % or less (including 0 mol %) based on all silicon atoms in the polyorganosiloxane.
- As the dimethylsiloxane used in producing a polyorganosiloxane, tri- or more-cyclic dimethylsiloxane-based cyclic bodies are listed, and tri to hepta-cyclic bodies are preferable. Specifically listed are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane and the like. These are used alone or in combination of two or more.
- The organosiloxane containing a vinyl-polymerizable functional group which can be used in production of a polyorganosiloxane contains a vinyl-polymerizable functional group and can be bonded to dimethylsiloxane via a siloxane bond. In view of reactivity with dimethylsiloxane, it is preferable to use various alkoxysilane compounds containing a vinyl-polymerizable functional group. Specifically listed are methacryloyloxysiloxane such as β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane and the like, vinyl siloxanes such as tetramethyltetravinylcyclotetrasiloxane and the like, p-vinylphenyldimethoxymethylsilane, further, mercaptosiloxanes such as γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane and the like. These organosiloxanes having a vinyl-polymerizable functional group can be used alone or in admixture of two or more.
- The size of a polyorganosiloxane is not particularly restricted, and the average particle size is preferably 600 nm or less, particularly 200 nm or less for the purpose of enhancing brightness after direct vapor deposition of the finally obtained resin composition.
- The method of producing a polyorganosiloxane is not particularly restricted, and the following method is mentioned as one example. First, in a mixture composed of dimethylsiloxane and an organosiloxane containing a vinyl-polymerizable functional group, an emulsifier and water are added and emulsified, to obtain latex. Then, this latex is finely granulated by using a homo-mixer of finely granulating by shearing force generated by high speed rotation, a homogenizer of finely granulating by injection force generated by a high pressure generator, and the like. Use of a high pressure emulsifying apparatus such as a homogenizer and the like is preferable since then the distribution of the particle size of the polyorganosiloxane latex is small. This latex after fine granulation is added in an acid aqueous solution containing an acid catalyst, and polymerized under high temperature. Termination of polymerization can be conducted by cooling the reaction solution, further, neutralizing the solution with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate and the like.
- Regarding addition of an acid catalyst, an acid catalyst may be previously mixed with a siloxane mixture, emulsifier and water, or an acid aqueous solution of high temperature may be dropped at a constant speed into latex in which a siloxane mixture has been finely granulated. However, it is preferable that latex in which a siloxane mixture has been finely granulated is dropped at a constant speed into an acid aqueous solution of high temperature, since then the particle size of the resulted polyorganosiloxane can be controlled easily.
- The polymerization time is, when an acid catalyst is mixed and granulated with a siloxane mixture, emulsifier and water before polymerization, preferably 2 hours or longer, particularly 4 hours or longer. In the case of the method in which latex in which a siloxane mixture has been finely granulated is dropped into an aqueous solution of an acid catalyst, it is preferable to keep the reaction solution for about 1 hour after completion of addition of the latex.
- The polymerization temperature is preferably 50° C. or more, particularly 80° C. or more. The upper limit of the polymerization temperature is not particularly restricted, and usually about 95° C.
- Preferable as the emulsifier used are anionic emulsifiers such as sodium alkylbenzensulfonates, sodium polyoxyethylene alkyl phenyl ether sulfates and the like, and of them, sulfonic acid-based emulsifiers such as sodium alkylbenzenesulfonates, sodium laurylsulfonate and the like are particularly preferable. These emulsifiers may be used alone or in combination of two or more. The use amount of an emulsifier is preferably 0.05 parts by weight or more based on 100 parts by weight of a siloxane mixture since then dispersed conditions is usually stable and emulsified condition of fine particles can be kept, and preferably 5 parts by weight or less based on 100 parts by weight of a siloxane mixture since then the color of a molded article is scarcely influenced by the color of an emulsifier itself or by deterioration of a resin composition ascribable to it.
- Listed as the acid catalyst used in polymerization of a polyorganosiloxane are sulfonic acids such as aliphatic sulfonic acids, aliphatic substituted benzenesulfonic acids, aliphatic substituted naphthalenesulfonic acids and the like, and mineral acids such as sulfuric acid, hydrochloric acid, nitric acid and the like. These acid catalysts may be used alone or in combination of two or more. As the acid catalyst, aliphatic substituted benzenesulfonic acids are preferable and n-dodecylbenzenesulfonic acid is particularly preferable because of excellent action of stabilizing polyorganosiloxane latex. When n-dodecylbenzenesulfonic acid is combined with a mineral acid such as sulfuric acid and the like, an influence exerted by the color of an emulsifier used in polyorganosiloxane latex on the color of a resin composition molded article can be suppressed to lower level. The addition amount thereof may be appropriately determined, and usually from about 0.1 to 20 parts by weight based on 100 parts by weight of a siloxane mixture.
- The (meth)acrylate-based polymer constituting the complex rubber-like polymer (G) used in the graft copolymer (A-I) is obtained by polymerizing an alkyl (meth)acrylate monomer, or a monomer mixture containing one or more alkyl(meth)acrylates. The (meth)acrylate-based polymer may contain other monomers than the alkyl (meth)acrylate monomer.
- Listed as the alkyl(meth)acrylate monomer are, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and the like, and alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate and the like. Of them, n-butyl acrylate is preferably used since then the resulted resin composition is excellent in impact resistance. These may be used alone or in combination of two or more.
- Polymerization can be conducted according to known methods. As described later, a graft crossing agent or cross-linking agent may be used.
- The method of producing a complex rubber-like polymer (G) used in the present invention is not particularly restricted, and there are listed a method in which separate latexes of a polyorganosiloxane and a (meth)acrylate-based polymer are hetero-aggregated or co-thickened, a method in which, in the presence of any one or more latexes, monomers (including also a mixture) forming other one or more polymers are polymerized and complexed, and other methods. Of them, a method is preferable in which (meth)acrylate monomers (including also a mixture) as described above are polymerized in the presence of an organosiloxane in the form of latex since then the resulted resin composition is excellent in impact resistance and brightness after direct vapor deposition.
- If necessary, it is also possible to use a graft crossing agent and a cross-linking agent in this procedure. Listed as the graft crossing agent and cross-linking agent which can be used are, for example, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and the like. These may be used alone or in combination of two or more. The addition amount thereof may be appropriately determined, and is preferably from about 0.3 to 6 parts by weight based on 100 parts by weight of (meth)acrylate monomers (including also a mixture) since then the resulted resin composition is excellent in impact resistance and brightness after direct vapor deposition.
- A monomer mixture constituted of these alkyl(meth) acrylates, and if necessary, a graft crossing agent and a cross-linking agent can be radical-polymerized in bulk, continuously or intermittently to a polyorganosiloxane in the form of latex, to obtain a polyorganosiloxane/(meth)acrylate-based complex rubber-like polymer (G).
- Regarding the ratio of polyorganosiloxane/(meth)acrylate-based polymer constituting a complex rubber-like polymer (G), it is preferable that the content of a polyorganosiloxane in a complex rubber-like polymer (G) is 1% by weight or more based on the total amount of a polyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture) since then the resulted resin composition is excellent in impact resistance. On the other hand, the content of a polyorganosiloxane in a complex rubber-like polymer (G) is preferably 99% by weight or less, more preferably 90% by weight or less based on the total amount of a polyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture) since then the resulted resin composition is excellent in balance of impact resistance and brightness after direct vapor deposition. When the amount of a polyorganosiloxane in a complex rubber-like polymer (G) is in this range, the resulted resin composition is excellent in impact resistance and brightness after direct vapor deposition. The amount of a polyorganosiloxane in a complex rubber-like polymer (G) is further preferably 2% by weight or more, particularly 3% by weight or more, and further preferably 50% by weight or less, particularly 10% by weight or less based on the total amount of a polyorganosiloxane and a (meth)acrylate-based polymer (monomer mixture).
- The average particle size of a complex rubber-like polymer (G) is not particularly restricted, and preferably less than 400 nm, further preferably 300 nm or less since then the resulted resin composition is excellent in bright appearance after direct vapor deposition. The lower limit of the average particle size of a complex rubber-like polymer (G) is not particularly restricted, and usually about 30 nm.
- It is preferable that the ratio of rubber-like polymers having a particle size of 500 nm or more is 4% by weight or less (including 0% by weight), particularly 3% by weight or less, further 2% by weight or less based on 100% by weight of all rubber-like polymers including a complex rubber-like polymer (G) since then a molded article having a beautiful bright appearance is obtained.
- The graft copolymer (A-I) can be produced by emulsion-graft-polymerizing vinyl-based monomers, preferably, at least one monomer component selected from the group consisting of aromatic alkenyl compounds, alkyl (meth)acrylates and vinyl cyanide compounds to a complex rubber-like polymer (G) described above.
- Of monomer components, styrene, α-methylstyrene, vinyltoluene and the like are listed, for example, as the aromatic alkenyl compound. As the alkyl(meth)acrylate, for example, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate and the like are listed. As the vinyl cyanide compound, for example, acrylonitrile, methacrylonitrile and the like are listed. Of them, a mixture of styrene and acrylonitrile is preferably used as the monomer component since then the resulted resin composition is excellent in impact resistance. The content of styrene in 100% by weight of this mixture is preferably 10% by weight or more, and preferably 90% by weight or less. On the other hand, it is preferable to use methyl methacrylate alone or a mixture containing methyl methacrylate in an amount preferably of 50% by weight or more since then the resulted resin composition is excellent in brightness after direct vapor deposition. These can be appropriately selected depending on the object.
- Regarding the weight ratio of a complex rubber-like polymer (G) and a vinyl-based monomer used in graft polymerization, in emulsion-graft-polymerization, it is preferable that the content of a complex rubber-like polymer (G) is 10% by weight or more and the content of a vinyl-based monomer is 90% by weight or less (in total: 100% by weight, the same in the followings) since then the finally resulted resin composition is excellent in impact resistance and also excellent in brightness after direct vapor deposition. On the other hand, regarding the weight ratio of a complex rubber-like polymer (G) and a vinyl-based monomer used in emulsion-graft-polymerization, it is preferable that the content of a complex rubber-like polymer (G) is 80% by weight or less and the content of a vinyl-based monomer is 20% by weight or more since then the finally resulted resin composition is excellent in impact resistance. When emulsion-graft-polymerization is conducted at such a weight ratio, the finally resulted resin composition is excellent in impact resistance, flowability and brightness after direct vapor deposition.
- Particularly, regarding the weight ratio of a complex rubber-like polymer (G) and a vinyl-based monomer used in emulsion-graft-polymerization, it is preferable that the content of a complex rubber-like polymer (G) is 30% by weight or more and the content of a vinyl-based monomer is 70% by weight or less, and it is preferable that the content of a complex rubber-like polymer (G) is 70% by weight or less and the content of a vinyl-based monomer is 30% by weight or less. When emulsion-graft-polymerization is conducted at such a weight ratio, the finally resulted resin composition manifests excellent impact resistance and direct vapor deposition appearance excellent in brightness in good balance.
- The graft copolymer (A-I) can be produced by radical polymerization using an emulsifier. In monomer components, various chain transfer agents for controlling the graft ratio and the molecular weight of graft components, for example, mercaptan-based compounds, terpene-based compounds, α-methylstyrene dimer and the like may be added. The polymerization conditions are not particularly restricted, and can be appropriately selected depending on necessity.
- As the radical polymerization initiator used in producing a graft copolymer (A-I) and a (meth)acrylate-based polymer in a complex rubber-like polymer (G) described above, peroxides, azo-based initiators, redox type initiators prepared by combining oxidizer and reducing agents, and the like can be used. Of them, redox type initiators are preferably used, and particularly, it is preferable to use redox type initiators combining ferrous sulfate . sodium pyrophosphate . glucose . hydroperoxide or ferrous sulfate . disodium ethylenediamine tetraacetate . rongalite . hydroperoxide.
- The emulsifier used in producing a graft copolymer (A-I) and a (meth)acrylate-based polymer in a complex rubber-like polymer (G) described above is not particularly restricted. Since an emulsifier used in production of a polyorganosiloxane is contained in a complex rubber-like polymer (G), this may be used itself, and if necessary, other emulsifiers may further be added. As the emulsifier which can be used in this case, it is preferable to use various salts of carboxylic acids such as sodium sarcocinate, fatty potassium, fatty sodium, dipotassium alkenylsuccinate, rosin soap and the like, and anionic emulsifiers such as alkyl sulfates, sodium alkylbenzenesulfonates, sodium polyoxyethylene alkylphenyl ether sulfate and the like since then the stability of latex in emulsion-polymerization is excellent and polymerization ratio is enhanced. These are classified and used depending on the object. Further, it may also be permissible that the emulsifier used in preparation of a complex rubber-like polymer (G) is used as it is and emulsifiers are not additionally added in emulsion-graft-polymerization.
- The graft copolymer (A-II) used in the present invention is obtained by graft-polymerizing one or more monomers or a monomer mixture including an alkyl (meth)acrylate as an essential component to a rubber-like polymer (R) in which the content of diene units is 30% by weight or less (including 0% by weight) in 100% by weight of all rubber-like polymers contained in a resin composition. The graft copolymer (A-II) may be used singly or in combination of two or more, and can be selected optionally depending on its application.
- The rubber-like polymer (R) which can be used is not particularly restricted excepting the above-mentioned conditions, and exemplified are diene-based rubber such as polybutadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, butyl acrylate-butadiene rubber and the like, acrylic rubber such as butyl acrylate rubber, butadiene-butyl acrylate rubber, 2-ethylhexyl acrylate-butyl acrylate rubber, 2-ethylhexyl methacrylate-butyl acrylate rubber, stearyl acrylate-butyl acrylate rubber, dimethylsiloxane-butyl acrylate rubber, silicone/butyl acrylate complex rubber and the like, polyolefin-based rubber polymers such as ethylene-propylene rubber, ethylene-propylene-diene rubber and the like, silicone-based rubber polymers such as polydimethylsiloxane rubber and the like. These can be used alone or in combination of two or more. Of course, the diene unit ratio is restricted in diene-based rubber.
- In these rubber-like polymers (R), the content of diene units in 100% by weight of all rubber-like polymers is 30% by weight or less, preferably 10% by weight or less, further preferably less than 1% by weight since then the resulted resin composition is excellent in weather resistance.
- It is preferable that the rubber-like polymer (R) contains at least one monomer of alkyl acrylates having an alkyl group containing 2 to 8 carbon atoms, more preferably 4 to 8 carbon atoms such as methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, 2-ethylhexyl acrylate and the like, and it is preferable that the ratio of alkyl acrylate units having an alkyl group containing 2 to 8 carbon atoms in the rubber-like polymer (R) is from 70 to 90% by weight since then the resulted resin composition is excellent in weather resistance, brightness after direct vapor deposition and the appearance of a hot plate welding connected part.
- Further, in the rubber-like polymer (R), copolymerizable vinyl-based monomers other than the above-mentioned monomers can be introduced in an amount of 30% by weight or less. Such vinyl-based monomers are not particularly restricted, and examples thereof include aromatic vinyl-based monomers such as styrene, α-methylstyrene, vinyltoluene and the like, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, graft crossing agents and cross-linking agents such as allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, divinylbenzene, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and the like, and other monomers. These may be used alone or in combination of two or more.
- The graft components of the graft copolymer (A-II) are composed of one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component, or one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component, and other vinyl-based monomers copolymerizable with them.
- Examples of the alkyl(meth)acrylate used include methyl(meth)acrylate, ethyl(meth)acrylate, n-propyl (meth)acrylate, n-butyl(meth)acrylate, 2-ethylhexyl (meth)acrylate and the like. These may be used alone or in combination of two or more. Of them, it is preferable to use methyl methacrylate since then the resulted resin composition is excellent in balance of impact resistance and brightness after direct vapor deposition.
- The copolymerizable other vinyl-based monomers are not particularly restricted, and the above-mentioned aromatic vinyl-based monomers, vinyl cyanide-based monomers and the like are listed.
- The content of an alkyl(meth)acrylate in 100% by weight of all graft components (the above-mentioned one or more monomers or a monomer mixture including a alkyl (meth)acrylate as an essential component, to be graft-polymerized to a rubber-like polymer (R)) is preferably from 20 to 100% by weight, more preferably from 50 to 100% by weight, further preferably from 70 to 100% by weight, particularly preferably from 80 to 100% by weight since then the resulted resin composition is excellent in weather resistance, and brightness after direct vapor deposition.
- The method of producing a graft copolymer (A-II) is not particularly restricted, and for example, a graft copolymer (A-II) can be produced by emulsion-graft-polymerizing one or more monomer components (one or more monomers or a monomer mixture) to the above-mentioned rubber-like polymer (R).
- Regarding the weight ratio of a rubber-like polymer (R) and one or more monomers or a monomer mixture used in graft polymerization, in emulsion-graft-polymerization, the content of a rubber-like polymer (R) in 100% by weight of a graft copolymer (A-II) is preferably 10% or more, more preferably 30% or more, and preferably 90% by weigh or less, more preferably 80% by weight or less. When emulsion-graft-polymerization is conduced at such a weight ratio, the finally resulted resin composition manifests excellent impact resistance and a direct vapor deposition appearance excellent in brightness, in good balance.
- The graft copolymer (A-II) can be produced by radical-polymerization using an emulsifier. Usually, a rubber-like polymer (R) is previously produced by emulsion-polymerization, and then one or more monomers or a monomer mixture as graft components are added to this rubber-like polymer latex, and they are graft-polymerized to obtain a graft copolymer (A-II). In monomer components, various chain transfer agents for controlling the graft ratio and the molecular weight of graft components, for example, mercaptan-based compounds, terpene-based compounds, α-methylstyrene dimer and the like may be added. The polymerization conditions are not particularly restricted, and can be appropriately selected depending on necessity.
- As the radical polymerization initiator used in producing a rubber-like polymer (R) and a graft copolymer (A-II), peroxides, azo-based initiators, redox type initiators prepared by combining oxidizer and reducing agents, and the like can be used. Of them, redox type initiators are preferably used, and particularly, it is preferable to use redox type initiators combining ferrous sulfate . sodium pyrophosphate . glucose . hydroperoxide or ferrous sulfate . disodium ethylenediamine tetraacetate . rongalite . hydroperoxide.
- The emulsifier used in producing a rubber-like polymer (R) and a graft copolymer (A-II) is not particularly restricted, it is preferable to use various salts of carboxylic acids such as sodium sarcocinate, fatty potassium, fatty sodium, dipotassium alkenylsuccinate, rosin soap and the like, and anionic emulsifiers such as alkyl sulfates, sodium alkylbenzenesulfonates, sodium polyoxyethylene alkylphenyl ether sulfate and the like since then the stability of latex in emulsion-polymerization is excellent and polymerization ratio is enhanced. These are classified and used depending on the object. Further, it may also be permissible that the emulsifier used in preparation of a rubber-like polymer (R) is used as it is and emulsifiers are not additionally added in emulsion-graft-polymerization.
- The latex of graft copolymers (A) obtained by emulsion-graft-polymerization [graft copolymers (A-I) and (A-II)] can be recovered as a graft copolymer (A) by, for example, a wet method in which it is added into hot water containing a dissolved coagulant to cause coagulation in the form of slurry, a spray dry method in which a graft copolymer (A) latex is sprayed into a heated atmosphere to recover a graft copolymer (A) semi-directly, and the other methods.
- As the coagulant used in the wet recovering method, inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and the like, and metal salts such as potassium chloride, calcium acetate, aluminum sulfate, alum and the like, can be used. The coagulant used is selected in a pair with an emulsifier used in polymerization. Namely, when carboxylic acid soaps such as fatty soaps and rosin soap and the like are only used as the emulsifier, a graft copolymer (A) can be recovered using any coagulant, however, when an emulsifier showing stable emulsification power also in an acid region such as a sodium alkylbenzenesulfonate is contained, the above-mentioned inorganic acids are insufficient, and it is necessary to use a metal salt as a coagulant.
- For obtaining a graft copolymer (A) in dry condition from a graft copolymer (A) in the form of slurry obtained by the wet recovering method, after a process such as a method in which first, a remaining emulsifier residue is eluted in water and washed, then, this slurry is dehydrated by centrifugation, press dehydrator and the like, then, dried by an air flow drier and the like or a method in which dehydration and drying are conducted simultaneously by a squeezing dehydrator, extruder and the like, a dried graft copolymer (A) can be obtained in the form of powder or granule. Further, in this procedure, it is also possible that which discharged from a squeezing dehydrator or extruder is carrier directly to an extruder or a molding machine for producing a resin composition, to give a molded article.
- The vinyl-based (co)polymer (B) which can be used in the resin composition of the present invention is a (co)polymer having as a constituent unit at least one selected from the group consisting of aromatic alkenyl units, vinyl cyanide units and alkyl(meth)acrylate units, namely, is a (co)polymer obtained by polymerizing monomers (also including a mixture) including any one or more of aromatic alkenyl compounds, vinyl cyanide compounds and alkyl(meth)acrylate compounds. By inclusion of the vinyl-based (co)polymer (B), other effects than the object of the present invention such as improvement in molding processability of the resulted resin composition, impartment of heat resistance, and the like can be obtained, and can be selected depending on its object.
- Further, the vinyl-based (co)polymer (B) may be a copolymer obtained by polymerizing a monomer mixture containing monomers other than aromatic alkenyl compounds, vinyl cyanide compounds and alkyl(meth)acrylate compounds, and for example, it is also preferable that the vinyl-based (co)polymer (B) is a copolymer obtained by polymerizing a monomer mixture composed of an aromatic alkenyl compound, vinyl cyanide compound and N-substituted maleimide.
- As the aromatic alkenyl units, vinyl cyanide units and alkyl(meth)acrylate units constituting them, the same compounds as those used in the above-mentioned graft polymerization can be used.
- As the other monomer components than these compounds, maleimide-based monomers, maleic anhydride and the like are listed. As the maleimide-based monomer, for example, maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmelaimide, N-propylmaleimide, N-cyclohexylmaleimide and the like are listed.
- As the vinyl-based (co)polymer (B), resins such as an acrylonitrile-styrene copolymer (SAN) resin, polymethyl methacrylate (PMMA) resin, styrene-methyl methacrylate copolymer (MS) resin, acrylonitrile-α methylstyrene copolymer (αSAN) resin, styrene-acrylonitrile-N-phenylmaleimide ternary copolymer (SAM) resin, polystyrene resin, acrylonitrile-styrene-methyl methacrylate ternary copolymer and the like are specifically preferable. The vinyl-based (co)polymer (B) may be used alone or in combination of two or more.
- A vinyl-based (co)polymer (B) having any molecular weight can be used.
- The polycarbonate (C) which can be used in the resin composition of the present invention is composed of a dihydroxydiarylalkane, and may be branched optionally. By inclusion of the polycarbonate (C), the heat resistance and impact resistance of the resulted resin composition can be improved.
- The dihydroxyarylalkane may have an alkyl group, chlorine atom or bromine atom at the ortho position to a hydroxyl group. Preferable as the dihydroxyarylalkane are 4,4′-dihydroxy-2,2′-diphenylpropane (bisphenol A), tetramethyl bisphenol A, bis(4-hydroxyphenyl)-p-diisopropylbenzene and the like.
- As the polycarbonate (C), those having any molecular weight can be used.
- The polycarbonate (C) can be produced by a known method, and in general, produced by reacting a dihydroxy compound or a polyhydroxy compound with a phosgene or a diester of carbonic acid.
- A branched polycarbonate is produced by substituting a part of a dihydroxy compound, for example, 0.2 to 2 mol % of this with a polyhydroxy compound. As the polyhydroxy compound, there are listed 1,4-bis(4′,4,2-dihydroxytriphenylmethyl)-benzene, phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)-heptene-2,4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tri(4-hydroxyphenyl)-benzene, 1,1,1-tri(4-hydroxyphenyl)-ethane, 2,2-bis[4,4′-(4,4′-dihydroxyphenyl)cyclohexyl]propane and the like.
- The polycarbonate (C) may be used alone or in combination of two or more.
- The polyester (C) which can be used in the resin composition of the present invention is mainly composed of a polyalkylene terephthalate, and preferably contains, in a ratio of 50% by weight or more, that composed of an aromatic dicarboxylic acid having 8 to 22 carbon atoms and an alkylene glycol or cycloalkylene glycol having 2 to 22 carbon atoms. By inclusion of the polyester (C), the molding processability and chemical resistance of the resulted resin composition can be improved.
- The polyester (C) may also contain, if necessary, an aliphatic dicarboxylic acid, for example, adipic acid, sebacic acid and the like, as a constituent unit, in an amount preferably of 80% by weight or less. Also, the polyester (C) may contain a polyalkylene glycol such as polyethylene glycol and the like as a constituent unit.
- As the polyester (C) used, polyethylene terephthalate, polytetramethylene terephthalate and the like are particularly preferable.
- As the polyester (C), those having any molecular weight can be used.
- The polyester (C) may be used alone or in combination of two or more.
- When these polycarbonates and polyesters are used, each of them may be used singly, or they may be used in any ratio, if necessary.
- In the direct vapor depositing resin composition of the present invention, other thermoplastic resins may be compounded in an amount within the range in which various abilities intended in the present invention are not significantly disturbed, if necessary.
- The other thermoplastic resin is not particularly restricted, and examples thereof include polyolefins such as polyvinyl chloride, polyethylene, polypropylene and the like, styrene-based elastomers such as styrene-butadiene-styrene (SBS), styrene-butadiene (SBR), hydrogenated SBS, styrene-isoprene-styrene (SIS) and the like, various olefin-based elastomers, various polyester-based elastomers, polyacetal resins, modified polyphenylene ethers (modified PPE resins), ethylene-vinyl acetate copolymer, PPS resin, PES resin, PEEK resin, polyallylate, liquid crystal polyester resins, polyamide resins (nylon) and the like, and ABS resins, ASA resins and styrene-acrylonitrile-silicone (SAS) resin and the like out of the range of the present invention. These other thermoplastic resins may be used alone or in combination of two or more.
- The use amount of these other thermoplastic resins is preferably 80 parts by weight or less in 100 parts by weight of a resin composition.
- The resin composition of the present invention can be produced by mixing and dispersing a graft copolymer (A), if necessary, a vinyl-based (co)polymer (B), polycarbonate and/or polyester (C), other thermoplastic resin by a V shaped blender or Henschel mixer and the like, and melt kneading this mixture by using an extruder or a kneader such as a Banbury mixer, press kneader, roll and the like.
- The resulted direct vapor depositing resin composition of the present invention can be used itself, or if necessary, after compounding of additives such as dyes, pigments, heat stabilizers, weather resistant aids, reinforcing agents, fillers, flame retardants, flame retardant aids, foaming agents, lubricants, plasticizers, antistatic additives and the like, as a production raw material of a molded article. The resin composition can be made into the intended molded article by various molding methods such as an injection molding method, extrusion molding method, blow molding method, compression molding method, calender molding method, inflation molding method and the like.
- The molded article made of the resin composition of the present invention which has been primary-processed by the above-mentioned various molding methods can be subjected to surface metallizing treatment with aluminum, chromium and the like by a vacuum vapor deposition method or sputtering method, without special pre-treatment such as formation of an undercoat-treated layer and the like, as described above. This metallized bright surface may be left as it is, however, for protecting the surface from generation of flaw by dust and the like, it is also possible to effect top coat treatment of forming a coat made of a silicon-based material and the like by painting and the like.
- As the industrial application examples of these resin compositions of the present invention, listed are automobile parts, particularly, housings of head lamps and tail lamps, domestic electric parts such as illumination equipment housings and the like, OA equipment housings, interior members and the like.
- The direct vapor depositing resin composition of the present invention is, particularly, suitable for lamp housings. A brightening-treated lamp housing molded article obtained by metallizing by direct vapor deposition of the surface of a molded article obtained by molding the direct vapor depositing resin composition of the present invention is made into contact with a resin made of a PC resin, PMMA resin and the like by a method such as hot plate welding, vibration welding and the like. The molded article of the present invention is particularly suitable for hot plate welding since it is excellent in stringing property.
- The following examples and comparative examples will illustrated the present invention further specifically, but do not limit the scope of the invention. % and parts in the following examples and comparative examples are by weight unless otherwise stated.
-
Octamethylcyclotetrasiloxane 98 parts γ-methacryloyloxypropyldimethoxymethylsilane 2 parts were mixed to obtain 100 parts of a siloxane-based mixture. To this was added an aqueous solution composed of sodium dodecylbenzenesulfonate 0.67 parts ion exchanged water 300 parts, and the mixture was stirred for 2 minutes by a homomixer at 10000 rotations/min., then, passed through a homogenizer under a pressure of 20 MPa, to obtain a stable pre-mixed organosiloxane latex. On the other hand, into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged dodecylbenzenesulfonic acid 10 parts ion exchanged water 90 parts, to prepare a 10% dodecylbenzenesulfonic acid aqueous solution. - This aqueous solution was heated to 85° C. and under this condition, previously mixed organosiloxane latex was dropped over 4 hours, and after completion of addition, its temperature was maintained for 1 hour, then, cooled to 40° C. or lower. Then, the reaction product was neutralized with a sodium hydroxide aqueous solution to pH 7, completing polymerization.
- Thus obtained polyorganosiloxane (L-1) latex was dried at 170° C. for 30 minutes, and the solid content was measured to find it was 17.7%. The average particle size of the polyorganosiloxane (L-1) in latex was 50 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more was about 0%. The content of organosiloxane units having a vinyl polymerizable functional group in polydimethylsiloxane was 0.65 mol %, and the content of silicon atoms having three or more siloxane bonds was 0 mol % based on all silicon atoms in polydimethylsiloxane.
-
Octamethylcyclotetrasiloxane 95.5 parts γ-methacryloyloxypropyldimethoxymethylsilane 0.5 parts tetraethoxysilane 4 parts were mixed to obtain 100 parts of a siloxane-based mixture. To this was added an aqueous solution composed of dodecylbenzenesulfonic acid 1 part sodium dodecylbenzenesulfonate 1 part ion exchanged water 200 parts, and the mixture was stirred for 2 minutes by a homomixer at 10000 rotations/min., then, passed through a homogenizer under a pressure of 20 MPa, to obtain a stable pre-mixed organosiloxane latex. - This pre-mixed organosiloxane latex was charged into a reactor equipped with a cooling tube, jacket heater and stirring apparatus, and the mixture was heated at 80° C. for 5 hours, then, cooled to about 20° C., and left as it was for 48 hours. Then, the reaction product was neutralized with a sodium hydroxide aqueous solution to pH 7, completing polymerization.
- Thus obtained polyorganosiloxane (L-2) latex was dried at 170° C. for 30 minutes, and the solid content was measured to find it was 36.5%. The average particle size of the polyorganosiloxane (L-2) in latex was 160 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more was 0.3%. The content of organosiloxane units having a vinyl polymerizable functional group in polydimethylsiloxane was 0.3 mol %, and the content of silicon atoms having three or more siloxane bonds was 1.5 mol % based on all silicon atoms in polydimethylsiloxane.
- Polymerization was conducted in the same manner as in Production Example 1 except that the siloxane mixture used was constituted of 96 parts of octamethylcyclotetrasiloxane, 2 parts of γ-methacryloyloxypropyldimethoxymethylsilane, and 2 parts of tetraethoxysilane, and as a result, the solid content was 17.3%, the average particle size was 50 nm, the ratio of rubber-like polymers having a particle size of 500 nm or more was about 0%, the content of methacryloxysiloxane units was 0.7 mol %, and the content of silicon atoms having three or more siloxane bonds was 1.2 mol %.
- Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged
polyorganosiloxane latex (L-1) produced in 8 parts Production Example 1 (solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, and they were mixed, then, to this was added a mixture composed of n-butyl acrylate 42 parts allyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.1 part t-butyl hydroperoxide 0.11 parts. The atmosphere was purged with nitrogen by passing a nitrogen flow through this reactor, the inner temperature was raised to 60° C., and at this point, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.000075 parts disodium ethylenediamine tetraacetate 0.000225 parts rongalite 0.2 parts ion exchanged water 10 parts was added, to initiate radical polymerization. By polymerization of the acrylate component, the liquid temperature rose to 78° C. This condition was maintained for 1 hour to complete polymerization of the acrylate component, obtaining latex of a complex rubber-like polymer of a polyorganosiloxane (L-1) with n-butyl acrylate rubber. - The average particle size of the complex rubber-like polymer was 120 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more in 100% by weight of this complex rubber-like polymer (solid) was 0.1%.
Further, the liquid temperature in the reactor lowered to 70° C., then, to this complex rubber latex was added an aqueous solution composed of rongalite 0.25 parts ion exchanged water 10 parts, then, as the first stage, a mixture of acrylonitrile 2.5 parts styrene 7.5 parts t-butyl hydroperoxide 0.05 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C. was kept for 1 hour, then, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.001 part disodium ethylenediamine tetraacetate 0.003 parts rongalite 0.2 parts Emal NC-35 (manufactured by Kao Corp.) 0.2 parts ion exchanged water 10 parts was added, then, as the second stage, a mixture of acrylonitrile 10 parts styrene 30 parts t-butyl hydroperoxide 0.2 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C. was kept for 0.5 hours, then, cumene hydroperoxide 0.05 parts was added, further, a condition of a temperature of 60° C. was kept for 0.5 hours, then, the mixture was cooled to obtain graft copolymer latex obtained by graft- polymerizing acrylonitrile and styrene to a complex rubber-like polymer composed of a polyorganosiloxane (L-1) and butyl acrylate rubber. - Then, 150 parts of a 1% calcium acetate aqueous solution was heated to 60° C., and into this was gradually dropped 100 parts of the latex of the graft copolymer, to cause coagulation. The precipitate was dehydrated, washed, and dried to obtain a polyorganosiloxane/acrylate complex rubber-based graft copolymer (A-I-1).
-
Polymerization was conducted in the same manner as in Production Example 4 except that the mixture in the first step was changed to acrylonitrile 5 parts styrene 15 parts t-butyl hydroperoxide 0.1 part, and the mixture in the second step was changed to methyl methacrylate 28.5 parts methyl acrylate 1.5 parts t-butyl hydroperoxide 0.15 parts, to give graft copolymer latex obtained by graft- polymerizing acrylonitrile and styrene in the first stage, and methyl methacrylate and methyl acrylate in the second stage, to a complex rubber-like polymer composed of a polyorganosiloxane (L-1) and butyl acrylate rubber. - Then, coagulation, dehydration, washing and drying were conducted in the same manner as in Production Example 4, to obtain a polyorganosiloxane/acrylate complex rubber-like graft copolymer (A-I-2).
- Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged
polyorganosiloxane latex (L-1) produced in 2 parts Production Example 1 (solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, and they were mixed, then, to this was added a mixture composed of n-butyl acrylate 48 parts allyl methacrylate 1.08 parts 1,3-butylene glycol dimethacrylate 0.36 parts t-butyl hydroperoxide 0.11 parts. - The atmosphere was purged with nitrogen by passing a nitrogen flow through this reactor, the inner temperature was raised to 60° C., and at this point, an aqueous solution composed of
ferrous sulfate hepta-hydrate 0.000075 parts disodium ethylenediamine tetraacetate 0.000225 parts rongalite 0.2 parts ion exchanged water 10 parts - was added, to initiate radical polymerization. By polymerization of the acrylate component, the liquid temperature rose to 80° C. This condition was maintained for 1 hour to complete polymerization of the acrylate component, obtaining latex of a complex rubber-like polymer of a polyorganosiloxane (L-1) with n-butyl acrylate rubber.
- The average particle size of the complex rubber-like polymer was 145 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more in 100% by weight of this complex rubber-like polymer (solid) was 0.3%.
- Graft polymerization was conducted in the same manner as in Production Example 4 excepting use of the resulted complex rubber, giving graft copolymer latex obtained by graft-polymerizing acrylonitrile and styrene to a complex rubber-like polymer composed of a polyorganosiloxane (L-1) and n-butyl acrylate rubber.
- Then, coagulation, dehydration, washing and drying were conducted in the same manner as in Production Example 4, to obtain a polyorganosiloxane/acrylate complex rubber-like graft copolymer (A-I-3).
- Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged
polyorganosiloxane latex (L-2) produced in 30 parts Production Example 2 (solid content) ion exchanged water (including water in (L-2)) 295 parts, and the reactor was purged with nitrogen, then, the reaction mixture was heated to 50° C., and to this was added a mixture composed of n-butyl acrylate 37.5 parts allyl methacrylate 2.5 parts t-butyl hydroperoxide 0.3 parts, and the mixture was stirred for 30 minutes. Then, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.0003 parts disodium ethylenediamine tetraacetate 0.001 part rongalite 0.17 parts ion exchanged water 5 parts - was added, to initiate radical polymerization. Thereafter, an inner temperature of 70° C. was maintained for 2 hours, to complete polymerization of the acrylate component, giving a complex rubber-like polymer latex of a polyorganosiloxane (L-2) and n-butyl acrylate.
- The average particle size of the complex rubber-like polymer was 190 nm, and the ratio of rubber-like polymers having a particle size of 500 nm or more in 100% by weight of this complex rubber-like polymer (solid) was 3%.
Into this complex rubber latex was dropped a mixture composed of acrylonitrile 9 parts styrene 21 parts t-butyl hydroperoxide 0.3 parts at an inner temperature of 70° C. over 45 minutes, then, a temperature of 70° C. was maintained for 4 hours, to complete graft polymerization to the complex rubber-like polymer. - Then, this graft copolymer latex was added into a 12% calcium chloride aqueous solution of the same amount (liquid temperature: 60° C.) while stirring, then, a temperature of 80° C. was kept for 5 minutes, further, a temperature of 95° C. was kept for 5 minutes, to cause coagulation. The precipitate was separated, washed, and dehydrated, then, dried at 85° C. for 24 hours, to obtain a polyorganosiloxane/acrylate complex rubber-like graft copolymer (A-I-4).
- Polymerization was conducted in the same manner as in Production Example 4 except that 50 parts (solid content) of the complex rubber-like polymer used was changed to 50 parts of a polyorganosiloxane (L-1, solid content), to give a graft copolymer (a-I-5) obtained by grafting acrylonitrile and styrene to a polyorganosiloxane.
-
Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged polybutadiene latex (average particle size: 50 parts 120 nm, ratio of particles having particle size of 500 nm or more: 0.2%) (solid content) at room temperature, and ion exchanged water (including water contained 140 parts in rubber-like polymer latex) glucose 0.6 parts anhydrous sodium pyrophosphate 0.01 part ferrous sulfate hepta-hydrate 0.005 parts sodium hydroxide 0.1 part were added, the reactor was purged with nitrogen while the reaction mixture was stirred, then, the reaction mixture was heated to 50° C. Into this was dropped a mixture composed of acrylonitrile 15 parts styrene 35 parts t-dodecylmercaptan 0.5 parts cumene hydroperoxide 0.3 parts over 180 minutes while controlling so that the inner temperature was not over 65° C. After completion of dropping, cumene hydroperoxide 0.12 parts was added, further, the mixture was maintained at the same temperature for 1 hour before cooling. Then, to the resulted latex was added antioxidant (Antage W-400, manufactured by 1 part, Kawaguchi Kagaku Kogyo K.K.) and the latex was added into a 1.2% sulfuric acid aqueous solution (liquid temperature: 70° C.) of the same amount as this graft copolymer latex to cause coagulation, further, the temperature was raised to 90° C. and kept for 5 minutes, then, the product was dehydrated, washed and dried to obtain a diene-based graft copolymer (a-I-6) in the form of opalescent powder. - Polymerization was conducted in the same manner as in Production Example 4 excepting that a polyorganosiloxane (L-1) was not used and the amount of n-butyl acrylate changed to 50 parts, giving a graft copolymer (a-I-7) obtained by grafting acrylonitrile and styrene to n-butyl acrylate rubber.
- The average particle size of the rubber-like polymer was 110 nm, and the ratio of particles having a particle size of 500 nm or more was about 0%.
- To 10 parts of polybutadiene latex having a solid content of 35% (pH 10, gel content: 85%, average particle size: 80 nm, solid content) was added 0.2 parts (solid content) of an acid group-containing copolymer latex having a solid content of 33% and an average particle size of 80 nm composed of 81.5% of a n-butyl acrylate unit and 18.5% of a methacrylic acid unit, and the mixture was stirred for 30 minutes, obtaining a thickened diene-based rubber-like polymer latex having an average particle size of 380 nm. To this was charged
dipotassium alkenylsuccinate 0.3 parts (Latemul ASK manufactured by Kao Corp., as substantial amount, the same in the followings) ion exchanged water (including water in thickened 175 parts, butadiene-based polymer latex) and to this was added a mixture composed of n-butyl acrylate 40 parts, allyl methacrylate 0.16 parts, 1,3-butylene glycol dimethacrylate 0.08 parts, t-butyl hydroperoxide 0.1 part while stirring. The atmosphere was purged with nitrogen by passing a nitrogen flow through this reactor, the inner temperature was raised to 60° C. When the inner liquid temperature reached 50° C., an aqueous solution composed of ferrous sulfate hepta-hydrate 0.00015 parts disodium ethylenediamine tetraacetate 0.00045 parts rongalite 0.24 parts ion exchanged water 5.0 parts was added, then, the inner temperature was raised to 75° C., to initiate radical polymerization. This condition was maintained for 1 hour to complete polymerization of the acrylate component, giving latex of a complex rubber- based rubber-like polymer of a thickened butadiene-based polymer with n-butyl acrylate rubber. The average particle size of this complex rubber-based rubber-like polymer latex was 300 nm, and the ratio of particles having a particle size of 500 nm or more was 51%. Then, an aqueous solution composed of rongalite 0.15 parts dipotassium alkenylsuccinate 0.65 parts ion exchanged water 10 parts was added, then, mixed liquid of acrylonitrile 6.3 parts styrene 18.7 parts t-butyl hydroperoxide 0.11 parts was dropped over 1 hour, to cause polymerization. 5 minutes after completion of dropping, an aqueous solution dissolving ferrous sulfate hepta-hydrate 0.001 part disodium ethylenediamine tetraacetate 0.003 parts rongalite 0.15 parts ion exchanged water 5 parts was added, then, mixed liquid of acrylonitrile 6.3 parts styrene 18.7 parts t-butyl hydroperoxide 0.19 parts n-octylmercaptan 0.014 parts was dropped over 1 hour, to cause polymerization. After completion of dropping, a condition of a temperature of 75° C. was kept for 10 minutes, then, the mixture was cooled, and when the inner temperature was reached 60° C., a dispersion composed of antioxidant (Antage W-500, manufactured by 0.2 parts Kawaguchi Kagaku Kogyo K.K.) dipotassium alkenylsuccinate 0.2 parts ion exchanged water 5 parts was added. The above-mentioned operation gave latex of a graft copolymer obtained by graft-polymerizing acrylonitrile/styrene to a complex rubber-based rubber- like polymer of a thickened butadiene-based polymer with n-butyl acrylate rubber. - Then, the above-mentioned polymer latex was added, while stirring, into a 0.6% sulfuric acid aqueous solution heated to 45° C. of an amount 1.2 fold of the whole latex, to coagulate a polymer. Then, the liquid temperature was raised to 65° C. and kept for 5 minutes, then, the liquid temperature was raised to 90° C. Then, the precipitate was separated, then, the recovered substance was added into water of 10-fold amount, then, stirred for 10 minutes, to effect washing treatment. This dispersion was dehydrated in a centrifugal dehydrator, further, dried at 80° C. for 16 hours, to obtain a graft copolymer (a-I-8).
- The average particle size and particle size distribution of the latexes described in the production examples were all measured by using a sub-micron particle size distribution measuring apparatus CHDF-2000 manufactured by MATEC APPLIED SCIENCES.
- An acrylic resin (B-1) composed of 99 parts of methyl methacrylate and 1 part of methyl acrylate and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.25 dl/g was produced by known suspension polymerization.
- An acrylonitrile-styrene copolymer (B-2) composed of 29 parts of acrylonitrile and 71 parts of styrene and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.60 dl/g was produced by known suspension polymerization.
- An acrylonitrile-styrene-N-phenylmaleimide ternary copolymer (B-3) composed of 19 parts of acrylonitrile, 53 parts of styrene and 28 parts of N-phenylmaleimide and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.65 dl/g was produced by known continuous solution polymerization.
- An acrylonitrile-amethylstyrene copolymer (B-4) composed of 25 parts of acrylonitrile and 75 parts of a methylstyrene and showing a reduced viscosity measured at 25° C. from a N,N-dimethylformamide solution of 0.50 dl/g was produced by known continuous solution polymerization.
- The graft copolymers (A-I-1) to (A-I-4), (a-I-5) to (a-I-8) produced in the production examples, vinyl-based (co)polymers (B-1) to (B-4) produced in the production examples, polycarbonate (C-1, manufactured by Mitsubishi Enpla K.K., trade name: Eupiron S2000F), polyester (C-2, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Tafpet N1300) were compounded in formulations shown in Tables 1 and 2 (numerical values in the tables are by weight), further, ethylenebisstearylamide was added in an amount of 0.4 parts based on 100 parts of these resin components, then, they were mixed using a Henschel mixer, and this mixture was fed to a deaerating type extruder (TEX-30 manufactured by Nippon Seikosho K.K.) having a barrel temperature of 230° C. or 260° C., and kneaded to obtain pellets.
- Using the resulted pellets, the Izod impact strength, weather resistance, brightness after direct vapor deposition, and hot plate welding property of the resin composition were measured and evaluated. The results are shown in Tables 1 and 2. Evaluations were conducted according to the following conditions.
- (1) Izod Impact Strength
- It was conducted by a method according to ASTM D256, and a notched Izod test piece having a thickness of ¼″ was left at 23° C. for 12 hours or longer, then, the impact strength was measured.
- (2) Weather Resistance
- A white-colored plate of 100 mm×100 mm×3 mm was treated for 1000 hours by Sunshine-weather-meter (manufactured by Suga Shikenki K.K.) at a black panel temperature of 63° C. and a cycle condition of 60 minutes (raining: 12 minutes). The weather resistance was evaluated by the degree of discoloration (AE) measured by a color difference meter in this case.
- (3) Brightness after Direct Vapor Deposition
- A plate of 100 mm×100 mm×3 mm was molded as a sample using an injection molding machine manufactured by Toshiba Machine Co., Ltd. “IS80FP” under conditions of a cylinder set temperature of 230° C., a mold temperature of 70° C. and an injection speed of 99%. Then, by a vacuum vapor deposition method, an aluminum vapor deposited film having a film thickness of about 50 nm was formed at a degree of vacuum of 1×10−6 Torr, an electric current value of 400 mA and a film formation speed of 1.5 mm/s. On this aluminum vapor deposited film, a top coat layer of SiO2 was vapor-deposited.
- Regarding the molded article thus obtained by direct vapor deposition, the regular reflectance (%) and diffusion reflectance (%) were measured using a reflectometer (“HR-100” manufactured by Murakami Shikisai Gijutsu Kenkyusho), and brightness was evaluated.
- (4) Hot Plate Welding Property
- A hot plate processed with a fluorine resin was heated at a surface temperature of 300° C., a test sheet (30 mm×100 mm×3 mm) was allowed to contact with this hot plate for 30 seconds, then, the test sheet was lifted vertically, and the stringing length in this operation was measured, and the hot plate welding property was evaluated. When the stringing length is less than 1 mm, the evaluation was ⊚, when 1 mm or more and less than 5 mm, the evaluation was , and when 5 mm or more, the evaluation was X.
- (5) Falling Weight Impact Resistance
- Using “Dupont impact tester” manufactured by Toyo Seiki Seisakusho, a weight of 1 kg was allowed to fall from a height of 1 mm on a sample plate of 100 mm×100 mm×3 mm under a punch diameter of {fraction (1/2)} inch and a cradle diameter of 3 inch, and cracked condition of the sample plate was observed. No cracking was evaluated as , and cracking was evaluated as X.
TABLE 1 Example Comparative Example 1 2 3 1 2 3 4 Resin Graft copolymer (A) (A-I-1) 36 composition (A-I-2) 36 (A-I-3) 36 (A-I-4) (a-I-5) 36 (a-I-6) 36 (a-I-7) 36 (a-I-8) Vinyl-based (co)polymer (B) (B-1) 29 29 29 29 29 29 100 (B-2) (B-3) 35 35 35 35 35 35 (B-4) Content 1) (%) 18 18 18 18 18 18 0 Ratio 2) (mol %) 0 0 0 0 — — — Average particle size 3) (nm) 120 120 145 50 120 110 — Ratio 4) (%) 0.1 0.1 0.3 0 0.2 0 — Material Izod impact strength [J/m] 130 110 110 100 130 110 30 properties Weather resistance ΔE 3.0 2.1 3.0 2.6 10.6 3.3 0.5 Brightness 5) Regular 6) (%) 81.8 82.5 82.9 81.9 81.8 82.1 83.0 Diffuse 7) (%) 0.9 0.7 0.7 1.6 1.5 1.6 0.6 Hot plate welding property ⊚ ⊚ ⊚ X ◯ X X Example 4 5 6 7 8 9 10 Resin Graft copolymer (A) (A-I-1) 36 36 36 27 24 32 80 composition (A-I-2) (A-I-3) (A-I-4) 9 (a-I-5) (a-I-6) 12 (a-I-7) (a-I-8) 4 Vinyl-based (co)polymer (B) (B-1) 64 22 30 26 29 20 (B-2) 29 (B-3) 35 35 35 35 (B-4) 42 Content 1) (%) 18 18 18 20 18 18 40 Ratio 2) (mol %) 0 0 0 0.5 0 0 0 Average particle size 3) (nm) 120 120 120 — — — 120 Ratio 4) (%) 0.1 0.1 0.1 1.0 0.1 5.8 0.1 Material Izod impact strength [J/m] 120 160 110 140 130 140 480 properties Weather resistance ΔE 2.2 4.1 3.8 3.0 6.3 3.4 2.6 Brightness 5) Regular 6) (%) 82.0 81.9 81.7 82.0 81.8 81.6 82.6 Diffuse 7) (%) 0.8 0.9 0.9 1.3 0.9 1.3 1.1 Hot plate welding property ⊚ ⊚ ◯ ⊚ ◯ ⊚ ◯ -
TABLE 2 Example Comparative Example 11 12 13 Example5 14 Resin Graft copolymer (A) (A-I-1) 20 15 15 20 composition (A-I-4) 5 (a-I-6) 5 20 Vinyl-based (co)polymer (B) (B-2) 30 30 30 30 30 Polycarbonate (C-1) 50 50 50 50 Polyester (C-2) 50 Content 1) (%) 10 11 10 10 10 Ratio 2) (mol %) 0 0.5 0 — 0 Average particle size 3) (nm) 120 — 120 120 120 Ratio 4) (%) 0.1 1.0 0.1 0.2 0.1 Material Izod impact strength [J/m] 620 610 610 580 210 properties Weather resistance ΔE 5.0 4.8 6.3 12.7 6.5 Brightness 5) Regular 6) (%) 82.2 81.9 82.0 82.1 82.3 Diffuse 7) (%) 0.9 1.2 0.9 1.6 1.1 Hot plate welding property ⊚ ⊚ ⊚ ◯ ◯ - The direct vapor depositing resin compositions of the present invention in Examples 1 to 14 had high Izod impact strength and excellent weather resistance, and showed excellent brightness revealing low diffusion reflectance after direct vapor deposition. Further, the stringing length in hot plate welding was short, and the hot plate welding property was also excellent.
- On the other hand, the resin compositions in Comparative Examples 1 to 5 were inferior in any one or more of the Izod impact resistance, weather resistance, and brightness after direct vapor deposition.
- As shown from Examples 1 and 7, there was a tendency that when the ratio of silicon atoms having three or more siloxane bonds in a polyorganosiloxane contained in a graft copolymer (A-I) is higher, the diffusion reflectance after direct vapor deposition increases and brightness deteriorates.
- Particularly when the ratio of rubber having a particle size of 500 nm or more in 100% by weight of the whole rubber-like polymer is 4% by weight or less as in Examples 1 to 8, 10 to 14, high Izod impact resistance, weather resistance and brightness after direct vapor deposition not known until now can be manifested.
-
Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged ion exchanged water 200 parts sodium carbonate 0.05 parts Phosphanol LO-529 (polyoxylethylene alkylphenyl 0.3 parts ether phosphate; manufactured by Toho Chemical Industry Co., Ltd.) rongalite 0.3 parts ferrous sulfate hepta-hydrate 0.000004 parts disodium ethylenediamine tetraacetate 0.000012 parts, and the atmosphere was purged with nitrogen by passing a nitrogen flow through this reactor while the reaction mixture was stirred, the inner temperature was raised to 70° C., and mixed liquid composed of styrene 12 parts n-butyl acrylate 50 parts allyl methacrylate 0.6 parts t-butyl hydroperoxide 0.19 parts Phosphanol LO-529 0.8 was dropped over 3 hours, and after completion of dropping, the mixture was further kept for 2 hours to obtain a rubber-like polymer. After that, an aqueous solution composed of rongalite 0.75 parts ion exchanged water 5 parts was added, then, mixed liquid composed of methyl methacrylate 36 parts methyl acrylate 2 parts t-butyl hydroperoxide 0.06 parts n-octylmercaptan 0.15 parts Phosphanol LO-529 0.3 parts was dropped over 1.5 hours. Thereafter, the mixture was kept for 30 minutes, to obtain graft copolymer latex. Then, 150 parts of a 1% calcium acetate aqueous solution was heated to 50° C., and into this was dropped 100 parts of the latex of the graft copolymer gradually to cause coagulation. This slurry was further heated to 95° C. and kept for 5 minutes, then, the precipitate was dehydrated, washed and dried, to obtain a graft copolymer (A-II-1) in the form of white powder. -
Polyorganosiloxane latex (L-1) produced in 8 parts Production Example 1 (solid content) Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, were added into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus, and mixed, then, to this was added a mixture composed of n-butyl acrylate 42 parts allyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.1 part t-butyl hydroperoxide 0.11 parts. The atmosphere was purged with nitrogen by passing a nitrogen flow through this reactor, the inner temperature was raised to 60° C., and at this point, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.000075 parts disodium ethylenediamine tetraacetate 0.000225 parts rongalite 0.2 parts ion exchanged water 10 parts was added, to initiate radical polymerization. By polymerization of the acrylate component, the liquid temperature rose to 78° C. This condition was maintained for 1 hour to complete polymerization of the acrylate component, obtaining latex of a complex rubber-like polymer of a polyorganosiloxane with n-butyl acrylate rubber. Further, the liquid temperature in the reactor lowered to 70° C., then, to this was added an aqueous solution composed of rongalite 0.25 parts ion exchanged water 10 parts, then, as the first stage, a mixture of methyl methacrylate 9.5 parts methyl acrylate 0.5 parts t-butyl hydroperoxide 0.05 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C. was kept for 1 hour, then, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.001 part disodium ethylenediamine tetraacetate 0.003 parts rongalite 0.2 parts Emal NC-35 (manufactured by Kao Corp.) 0.2 parts ion exchanged water 10 parts was added, then, as the second stage, a mixture of methyl methacrylate 38 parts methyl acrylate 2 parts t-butyl hydroperoxide 0.2 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C. was kept for 0.5 hours, then, cumene hydroperoxide 0.05 parts was added, further, a condition of a temperature of 60° C. was kept for 0.5 hours, then, the mixture was cooled to obtain graft copolymer latex obtained by graft- polymerizing methyl methacrylate and methyl acrylate to a complex rubber-like polymer composed of a polyorganosiloxane and butyl acrylate rubber. - Then, 150 parts of a 1% calcium acetate aqueous solution was heated to 60° C., and into this was gradually dropped 100 parts of the latex of the graft copolymer, to cause coagulation. The precipitate was dehydrated, washed, and dried to obtain a graft copolymer (A-II-2).
-
Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged ferric sulfate hepta-hydrate 0.00004 parts disodium ethylenediamine tetraacetate 0.00012 parts rongalite 0.2 parts ion exchanged water 190 parts and the mixture was heated to 80° C. while stirring under a nitrogen flow. To this was added {fraction (1/10)} of a mixture composed of methyl methacrylate 12.1 parts methyl acrylate 10.9 parts styrene 1.1 parts ethylene glycol dimethacrylate 0.8 parts allyl methacrylate 0.1 part t-butyl hydroperoxide 0.1 part Phosphanol LO-529 0.8 parts and kept for 15 minutes, then, remaining {fraction (9/10)} of the mixture was dropped over 3 hours to cause polymerization, then, the reaction mixture was kept for 1 hour at 80° C. without change, to effect polymerization of the innermost layer (core part). Then, to this core part latex was added an aqueous solution composed of 0.2 parts of rongalite and 5 parts of ion exchanged water, further, a mixture composed of n-butyl acrylate 30.6 parts styrene 6.3 parts ethylene glycol dimethacrylate 0.1 part diallyl malate 0.5 parts t-butyl hydroperoxide 0.12 parts Phosphanol LO-529 0.7 parts was dropped over 3 hours to cause polymerization, then, the reaction mixture was further kept for 2 hours at 80° C. without change, to effect polymerization of the intermediate layer (rubber part). Then, in the presence of this latex, an aqueous solution composed of 0.12 parts of rongalite and 5 parts of ion exchanged water was added, then, a mixture composed of methyl methacrylate 35.5 parts methyl acrylate 2.0 parts t-dodecylmercaptan 0.2 parts t-butyl hydroperoxide 0.1 part was dropped over 2 hours to cause polymerization, then, the reaction mixture was further kept for 1 hour at 80° C. without change, to effect polymerization of the outermost layer (graft part), obtaining latex of a graft copolymer (A-II-3) having a three-layer structure. - This latex was coagulated and recovered in the same manner as for the graft copolymer (A-II-1) in Production Example 16, to obtain a graft copolymer (A-II-3) which is a white powder.
-
Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was added polyorganosiloxane latex (L-3) (solid content) 8 parts Emal NC-35 (polyoxyethylene alkylphenyl ether 0.2 parts sulfate; manufactured by Kao Corp.) ion exchanged water 148.5 parts, and these were mixed, then, a mixture composed of n-butyl acrylate 42 parts allyl methacrylate 0.3 parts 1,3-butylene glycol dimethacrylate 0.1 part t-butyl hydroperoxide 0.11 parts was added. The atmosphere was purged with nitrogen by passing a nitrogen flow through this reactor, the inner temperature was raised to 60° C., and at this point, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.000075 parts disodium ethylenediamine tetraacetate 0.000225 parts rongalite 0.2 parts ion exchanged water 10 parts was added, to initiate radical polymerization. By polymerization of the acrylate component, the liquid temperature rose to 78° C. This condition was maintained for 1 hour to complete polymerization of the acrylate component, obtaining latex of a complex rubber-like polymer of a polyorganosiloxane with n-butyl acrylate rubber. Further, the liquid temperature in the reactor lowered to 70° C., then, to this was added an aqueous solution composed of rongalite 0.25 parts ion exchanged water 10 parts, then, as the first stage, a mixture of methyl methacrylate 9.5 parts methyl acrylate 0.5 parts t-butyl hydroperoxide 0.05 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C. was kept for 1 hour, then, an aqueous solution composed of ferrous sulfate hepta-hydrate 0.001 part disodium ethylenediamine tetraacetate 0.003 parts rongalite 0.2 parts Emal NC-35 (manufactured by Kao Corp.) 0.2 parts ion exchanged water 10 parts was added, then, as the second stage, a mixture of methyl methacrylate 38 parts methyl acrylate 2 parts t-butyl hydroperoxide 0.2 parts was dropped over 2 hours, to effect polymerization. After completion of dropping, condition of a temperature of 60° C. was kept for 0.5 hours, then, cumene hydroperoxide 0.05 parts was added, further, a condition of a temperature of 60° C. was kept for 0.5 hours, then, the mixture was cooled to obtain graft copolymer latex obtained by graft- polymerizing methyl methacrylate and methyl acrylate to a complex rubber-like polymer composed of a polyorganosiloxane and butyl acrylate rubber. - Then, 150 parts of a 1% calcium acetate aqueous solution was heated to 60° C., and into this was gradually dropped 100 parts of the latex of the graft copolymer, to cause coagulation. The precipitate was dehydrated, washed, and dried to obtain a graft copolymer (A-II-4).
-
Into a reactor equipped with a reagent injection vessel, cooling tube, jacket heater and stirring apparatus was charged polybutadiene latex (average particle size: 50 parts 290 nm) (solid content) at room temperature, and to this was added ion exchanged water (including water contained 140 parts in rubber-like polymer latex) glucose 0.6 parts anhydrous sodium pyrophosphate 0.01 part ferrous sulfate hepta-hydrate 0.005 parts sodium hydroxide 0.1 part and the atmosphere was purged with nitrogen while the reaction mixture was stirred, then the reaction mixture was raised to 50° C., into this was dropped a mixture composed of acrylonitrile 15 parts styrene 35 parts t-dodecylmercaptan 0.5 parts cumene hydroperoxide 0.3 parts over 180 minutes, and controlled so that the inner temperature was not over 65° C. After completion of dropping, cumene hydroperoxide 0.12 parts was added, further, the reaction mixture was kept for 1 hour before cooling. Then, to the resulted latex was added antioxidant (Antage W-400, manufactured by 1 part, Kawaguchi Kagaku Kogyo K.K.) and the latex was added into a 1.2% sulfuric acid aqueous solution (liquid temperature: 70° C.) of the same amount as this graft copolymer latex to cause coagulation, further, the temperature was raised to 90° C. and kept for 5 minutes, then, the product was dehydrated, washed and dried to obtain a graft copolymer (a-II-5) in the form of opalescent powder. - Polymerization was conducted in the same manner as in Production Example 17 excepting that methyl methacrylate and methyl acrylate used in the first stage were changed to 2.5 parts of acrylonitrile and 7.5 parts of styrene, and methyl methacrylate and methyl acrylate used in the second stage were changed to 10 parts of acrylonitrile and 30 parts of styrene, obtaining graft copolymer latex obtained by graft-polymerizing acrylonitrile and styrene to a complex rubber-like polymer composed of a polyorganosiloxane and butyl acrylate rubber.
- Then, coagulation, dehydration, washing and drying were conducted in the same manner as in Production Example 17 to obtain a graft copolymer (a-II-6).
-
Into a stainless autoclave equipped with a reagent injection vessel, water cooling jacket heater and stirring apparatus was charged ion exchanged water 190 parts n-butyl acrylate 50 parts beef fatty potassium 1 part sodium N-lauroylsarcosinate 0.5 parts diisopropylbenzene hydroperoxide 0.2 parts anhydrous sodium sulfate 0.2 parts and the atmosphere was purged with nitrogen while the reaction mixture was stirred. Further, 1,3-butadiene 50 parts was charged, and the inner temperature was raised to 40° C. Then, a mixture composed of ion exchanged water 10 parts dextrose 0.2 parts rongalite 0.05 parts anhydrous sodium pyrophosphate 0.2 parts disodium ethylenediamine tetraacetate 0.001 part ferrous sulfate hepta-hydrate 0.003 parts was added, to cause polymerization. The inner temperature was raised to 50° C. by polymerization heat generation and temperature rising, and the jacket was controlled so that the temperature was constant at this temperature, finally, polymerization was completed in 9 hours, obtaining a rubber-like polymer having an average particle size of 105 nm. Then, into a reactor equipped with a cooling tube, jacket heater and stirring apparatus was charged the following components under nitrogen flow, and the mixture was heated to an inner temperature of 65° C. while stirring. potassium oleate 2.2 parts sodium dioctylsulfosuccinate (70% solution) 3.6 parts sodium formaldehyde sulfoxylate di-hydrate 0.3 parts ferrous sulfate hepta-hydrate 0.003 parts disodium ethylenediamine tetraacetate 0.009 parts ion exchanged water 200 parts. To this was added a mixture composed of n-butyl acrylate 81.5 parts methacrylic acid 18.5 parts cumene hydroperoxide 0.5 parts over 2 hours, and also after completion of addition, polymerization was continued at the same temperature for 2 hours, to obtain an acid group-containing copolymer latex for thickening having an average particle size of 150 nm. 70 parts (solid content) of the resulted rubber- like polymer latex was charged into a reactor equipped with a cooling tube, jacket heater and stirring apparatus, the content was stirred at room temperature, and pH was controlled to 9.2 with a 2% sodium carbonate aqueous solution. Further, 1.2 parts of the acid group- containing copolymer latex (solid content) was charged, stirring was continued for 30 minutes for thickening treatment, obtaining thickened rubber-like polymer latex having an average particle size of 190 nm. Further, while continuing stirring, ion exchanged water (also including water in 200 parts rubber-like polymer latex) rongalite 0.14 parts sodium N-lauroylsarcosinate 0.35 parts were added, the inner temperature was raised to 75° C., and a mixture of the following compounds was continuously added over 90 minutes, for polymerization. methyl methacrylate 28.8 parts ethyl acrylate 1.2 parts n-ocrylmercaptan 0.05 parts cumene hydroperoxide 0.12 parts. - After completion of addition, the inner temperature was kept at this temperature further for 60 minutes, completing polymerization.
- To the resulted graft copolymer latex was added 0.4 parts of styrenated phenol, 0.3 parts of dilauryl thiopropionate and 0.4 parts of triphenyl phosphite, then, a 0.25% dilute sulfuric acid aqueous solution heated to 50° C. of an amount 2-fold of the graft latex was added to precipitate a graft copolymer, further, thermally treated at 90° C. for 5 minutes, then, washed with water, and dehydration thereof was repeated several times, and finally dried to obtain a graft copolymer (a-II-7) which is a white powder.
- Polymerization was conducted in the same manner as in Production Example 16 excepting that 36 parts of methyl methacrylate and 2 parts of methyl acrylate used in graft polymerization was changed to 10 parts of acrylonitrile and 28 parts of styrene, obtaining graft copolymer latex obtained by graft-polymerizing acrylonitrile and styrene to butyl acrylate rubber.
- Then, coagulation, dehydration, washing and drying were conducted in the same manner as in Production Example 16 to obtain a graft copolymer (a-II-8).
- The graft copolymers (A-II-1) to (A-II-4), (a-II-5) to (a-II-8), (a-I-8) produced in the production examples, polymers (B-1) to (B-4) produced in the production examples, polycarbonate (C-1, manufactured by Mitsubishi Enpla K.K., trade name: Eupiron S2000F), polyester (C-2, manufactured by Mitsubishi Rayon Co., Ltd., trade name: Tafpet N1300) were compounded in formulations shown in Tables 3 and 4 (numerical values in the tables are by weight), further, ethylenebisstearylamide was added in an amount of 0.4 parts based on 100 parts of these resin components, then, they were mixed using a Henschel mixer, and this mixture was fed to a deaerating type extruder (TEX-30 manufactured by Nippon Seikosho K.K.) having a barrel temperature of 230° C. or 260° C., and kneaded to obtain pellets.
- Using the resulted pellets, the Izod impact strength, weather resistance, brightness after direct vapor deposition, and hot plate welding property of the resin composition were measured and evaluated as described above. The results are shown in Tables 3 and 4.
TABLE 3 Example Comparative Example 15 16 17 6 7 8 9 Resin Graft copolymer (A) (A-II-1) 29 composition (A-II-2) (A-II-3) 40 (A-II-4) 36 (a-II-5) 36 (a-II-6) (a-II-7) 26 (a-II-8) 29 (a-I-8) Vinyl-based (co)polymer (B) (B-1) 100 (B-2) 71 60 64 64 71 74 (B-3) (B-4) Ratio 8) 0 0 0 100 0 50 0 Ratio 9) 100 100 100 0 0 100 — Material Falling weight impact strength ◯ ◯ ◯ ◯ ◯ ◯ X properties Weather resistance ΔE 3.0 3.1 2.8 12.3 3.7 5.6 0.5 Brightness 5) Regular 6) (%) 82.6 82.6 82.8 82.3 81.4 81.9 83.0 Diffuse 7) (%) 1.0 1.2 1.3 1.6 1.9 1.8 0.8 Hot plate welding property ⊚ ⊚ ⊚ ◯ ◯ X X Example 18 19 20 21 22 23 24 Resin Graft copolymer (A) (A-II-1) 29 29 29 23 23 23 composition (A-II-2) 36 (A-II-3) (A-II-4) (a-II-5) 8 (a-II-6) 8 (a-II-7) (a-II-8) (a-I-8) 8 Vinyl-based (co)polymer (B) (B-1) 36 (B-2) 35 39 32 69 69 69 64 (B-3) 32 (B-4) 39 Ratio 8) 0 0 0 22 0 9 0 Ratio 9) 100 100 100 70 70 70 100 Material Falling weight impact strength ◯ ◯ ◯ ◯ ◯ ◯ ◯ properties Weather resistance ΔE 2.6 3.2 3.0 3.4 3.1 3.6 2.8 Brightness 5) Regular 6) (%) 82.1 81.9 82.1 81.5 82.3 81.7 82.8 Diffuse 7) (%) 0.9 1.1 1.0 1.1 1.1 1.3 1.0 Hot plate welding property ⊚ ⊚ ◯ ◯ ⊚ ◯ ⊚ -
TABLE 4 Comparative Example Example Example 25 26 10 11 27 Resin Graft copolymer (A) (A-II-1) 20 15 20 composition (a-II-5) 5 25 (a-II-7) 18 Vinyl-based (co)polymer (B) (B-2) 30 30 25 32 30 Polycarbonate (C) (C-1) 50 50 50 50 Polyester (C) (C-2) 50 Ratio 8) 0 21 100 50 0 Ratio 9) 100 70 0 100 100 Material Falling weight impact strength ◯ ◯ ◯ ◯ ◯ properties Weather resistance ΔE 3.9 4.2 13.2 8.2 4.5 Brightness 5) Regular 6) (%) 82.3 81.9 81.6 81.9 82.0 Diffuse 7) (%) 1.1 1.2 1.6 1.7 1.2 Hot plate welding property ⊚ ⊚ ◯ X ◯ - The resin compositions of the present invention in Examples 15 to 27 had excellent weather resistance, and showed excellent brightness revealing low diffusion reflectance after direct vapor deposition. Further, the stringing length in hot plate welding was short, and the hot plate welding property was also excellent.
- On the other hand, the resin compositions in Comparative Examples 6 to 11 were inferior in any one or more of the weather resistance, brightness after direct vapor deposition and hot plate welding property.
- As shown in Examples 15 to 27, the ratio of methyl methacrylate in the grafted part composition (100% by weight) of a graft copolymer contained in the resin composition is preferably from 70 to 100% by weight.
- According to the present invention, a direct vapor depositing resin composition capable of providing a beautiful bright appearance after direct vapor deposition of a metal, further, having high level mechanical strengths such as impact strength and the like, and weather resistance, and also excellent in hot plate welding property with a transparent resin such as PMMA resins, polycarbonate resins and the like, and a molded article obtained by using this resin composition, can be provided.
- Particularly, balance of weather resistance, brightness after direct vapor deposition and hot plate welding property is extremely excellent as compared with conventionally known rubber-modified resin compositions, and the direct vapor depositing resin composition of the present invention provides an extremely high utility value as various industrial materials.
Claims (13)
1. A direct vapor depositing resin composition comprising at least one selected from the group consisting of the following graft copolymers (A-I) and (A-II).
(A-I): A graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture to a complex rubber-like polymer (G) composed of a polyorganosiloxane and a (meth)acrylate-based polymer.
(A-II): A graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture including an alkyl(meth)acrylate as an essential component to a rubber-like polymer (R) in which the content of diene units is 30% by weight or less (including 0% by weight) in 100% by weight of the whole rubber-like polymer.
2. The direct vapor depositing resin composition according to claim 1 wherein the composition comprises a vinyl-based (co)polymer (B) having as a constituent unit at least one selected from the group consisting of aromatic alkenyl units, vinyl cyanide units and alkyl (meth)acrylate units.
3. The direct vapor depositing resin composition according to claim 2 wherein the total content of said graft copolymers (A-I) and (A-II) is from 5 to 95% by weight based on the total amount of the graft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer (B), and the content of the vinyl-based (co)polymer (B) is from 95 to 5% by weight based on the total amount of the graft copolymers (A-I) and (A-II) and the vinyl-based (co)polymer (B).
4. The direct vapor depositing resin composition according to any of claims 1 to 3 wherein the composition comprises a polycarbonate and/or polyester (C).
5. The direct vapor depositing resin composition according to claim 4 wherein the total content of said graft copolymers (A-I) and (A-II) is from 5 to 80% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C), the content of said vinyl-based (co)polymer (B) is from 75 to 0% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C), and the content of said polycarbonate and/or polyester (C) is from 95 to 20% by weight based on the total amount of the graft copolymers (A-I) and (A-II), vinyl-based (co)polymer (B) and polycarbonate and/or polyester (C).
6. The direct vapor depositing resin composition according to any of claims 1 to 5 wherein the composition comprises said graft copolymer (A-I) and, in this graft copolymer (A-I), the ratio of rubber-like polymers having a particle size of 500 nm or more is less than 4% by weight, in all rubber-like polymers including a complex rubber-like polymer (G).
7. The direct vapor depositing resin composition according to any of claims 1 to 6 wherein the composition comprises said graft copolymer (A-I) and, in this graft copolymer (A-I), the content of a polyorganosiloxane in a complex rubber-like polymer (G) is from 1 to 99% by weight based on the total amount of a polyorganosiloxane and a (meth)acrylate-based polymer.
8. The direct vapor depositing resin composition according to any of claims 1 to 7 wherein the composition comprises said graft copolymer (A-I) and this graft copolymer (A-I) is a graft copolymer obtained by graft-polymerizing one or more monomers or a monomer mixture to a complex rubber-like polymer (G) composed of a (meth)acrylate-based polymer and a polyorganosiloxane in which the content of silicon atoms having three or more siloxane bonds is 1 mol % or less (including 0 mol %) based on all silicon atoms in polydimethylsiloxane.
9. The direct vapor depositing resin composition according to any of claims 1 to 8 wherein the composition comprises said graft copolymer (A-II) and, in this graft copolymer (A-II), the rubber-like polymer (R) contains as a constituent unit at least one of alkyl acrylate units having an alkyl group containing 2 to 8 carbon atoms.
10. The direct vapor depositing resin composition according to any of claims 1 to 8 wherein the composition comprises said graft copolymer (A-II) and, in this graft copolymer (A-II), said one or more monomers or a monomer mixture containing an alkyl(meth)acrylate as an essential component to be graft-polymerized to the rubber-like polymer (R) contains an alkyl(meth)acrylate in an amount of 50 to 100% by weight.
11. A molded article obtained by molding the direct vapor depositing resin composition according to any of claims 1 to 10 .
12. A molded article according to claim 11 wherein its surface is metallized by direct vapor deposition.
13. A lamp housing obtained by metallization by direct vapor deposition of the surface of a molded article obtained by molding the direct vapor depositing resin composition according to any of claims 1 to 10 .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/716,646 US7910028B2 (en) | 2001-08-10 | 2010-03-03 | Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001243941 | 2001-08-10 | ||
JP2001-243941 | 2001-08-10 | ||
PCT/JP2002/008044 WO2003016399A1 (en) | 2001-08-10 | 2002-08-07 | Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/716,646 Continuation US7910028B2 (en) | 2001-08-10 | 2010-03-03 | Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040249069A1 true US20040249069A1 (en) | 2004-12-09 |
Family
ID=33486986
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/485,117 Abandoned US20040249069A1 (en) | 2001-08-10 | 2002-08-07 | Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing |
US12/716,646 Expired - Fee Related US7910028B2 (en) | 2001-08-10 | 2010-03-03 | Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/716,646 Expired - Fee Related US7910028B2 (en) | 2001-08-10 | 2010-03-03 | Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing |
Country Status (2)
Country | Link |
---|---|
US (2) | US20040249069A1 (en) |
CN (1) | CN1733964B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050079928A1 (en) * | 2003-10-07 | 2005-04-14 | Bridgestone Sports Co., Ltd. | Rubber composition for golf ball and golf ball |
WO2006052437A1 (en) * | 2004-11-04 | 2006-05-18 | General Electric Company | Method for reducing stringiness of a resinous composition during hot plate welding |
US20090036607A1 (en) * | 2005-03-03 | 2009-02-05 | Mitsubishi Rayon Co., Ltd. | Polymer particle, resin composition containing same, and molded body |
EP2182016A1 (en) * | 2007-07-13 | 2010-05-05 | Mitsubishi Rayon Co. Ltd. | Graft copolymer, thermoplastic resin composition, and molded object |
US8691915B2 (en) | 2012-04-23 | 2014-04-08 | Sabic Innovative Plastics Ip B.V. | Copolymers and polymer blends having improved refractive indices |
EP3369755A4 (en) * | 2015-10-28 | 2019-10-23 | UMG ABS, Ltd. | Graft copolymer, crosslinked particles, graft crosslinked particles, rubbery polymer and thermoplastic resin composition using same |
US11161974B2 (en) * | 2017-06-06 | 2021-11-02 | Mitsubishi Chemical Corporation | Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition, and molded article |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2944717B1 (en) * | 2009-04-27 | 2012-08-17 | Peugeot Citroen Automobiles Sa | METHOD FOR PARTIALLY METALLIZING A PIECE OF PLASTIC MATERIAL, PARTICULARLY A MASK OF LIGHTING LIGHT AND / OR SIGNALING OF A VEHICLE. |
CN102135249A (en) * | 2011-01-30 | 2011-07-27 | 厦门莱肯照明科技有限公司 | Led lamp device |
CN103160105A (en) * | 2011-12-19 | 2013-06-19 | 海洋王(东莞)照明科技有限公司 | Makrolon composite material and lamp |
CN104864288A (en) * | 2015-05-08 | 2015-08-26 | 欧普照明股份有限公司 | Lamp |
CN107364205B (en) * | 2017-07-12 | 2019-06-04 | 东莞市瑞年塑胶科技有限公司 | One kind is aluminized lampshade material and its manufacture craft |
CN110229570A (en) * | 2019-06-18 | 2019-09-13 | 袁振鹏 | A kind of protection wax and its preparation process for preventing statue in bronze from generating verdigris |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4894415A (en) * | 1986-09-11 | 1990-01-16 | Mitsubishi Rayon Co., Ltd. | Polyphenylene ether resin composition |
US5043405A (en) * | 1988-01-07 | 1991-08-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Methacrylic copolymer having low moisture absorption properties |
US5132191A (en) * | 1990-10-26 | 1992-07-21 | General Electric Company | Polymer surfaces for subsequent plating thereon and improved metal-plated plastic articles made therefrom |
US5275882A (en) * | 1992-02-03 | 1994-01-04 | General Electric Company | Method for improving adhesion of aluminum layers to thermoplastics and article |
US5391648A (en) * | 1990-07-24 | 1995-02-21 | Mitsubishi Rayon Co., Ltd. | Polyorganosiloxane graft copolymers |
US5498440A (en) * | 1992-01-21 | 1996-03-12 | General Electric Company | Adhesion of electroless coating to resinous articles |
US5543460A (en) * | 1992-02-06 | 1996-08-06 | Mitsubishi Rayon Co., Ltd. | Graft copolymer particles their production and compositions comprising them |
US5804655A (en) * | 1995-09-12 | 1998-09-08 | Kaneka Corporation | Silicone-modified acrylic rubber particles, graft copolymer particles of silicone-modified acrylic rubber and thermoplastic resin composition |
US20040063814A1 (en) * | 2001-02-09 | 2004-04-01 | Nobuo Miyatake | Impact modifier for thermoplastic resin and resin composition containing the same |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3733838A1 (en) * | 1987-10-07 | 1989-04-20 | Basf Ag | GLASS FIBER AMPLIFIED THERMOPLASTIC MOLDINGS BASED ON POYESTERS AND POLYMERPROPYLENE |
JP2529509B2 (en) | 1992-05-07 | 1996-08-28 | 筒中プラスチック工業株式会社 | Vinyl chloride resin composition |
JP3142686B2 (en) | 1992-09-21 | 2001-03-07 | 三菱レイヨン株式会社 | Vinyl chloride resin composition |
JP3124418B2 (en) | 1992-09-29 | 2001-01-15 | 三菱レイヨン株式会社 | Polyester resin composition |
JPH11199642A (en) | 1998-01-16 | 1999-07-27 | Mitsubishi Rayon Co Ltd | Graft copolymer and resin composition containing the same |
JP2000204220A (en) * | 1999-01-13 | 2000-07-25 | Kanegafuchi Chem Ind Co Ltd | Modifier for methacrylic resin |
JP4438128B2 (en) | 1999-06-21 | 2010-03-24 | ユーエムジー・エービーエス株式会社 | Direct vapor deposited thermoplastic resin molded product |
JP2001200132A (en) | 2000-01-19 | 2001-07-24 | Mitsubishi Rayon Co Ltd | Flame-retarded resin composition |
JP4580493B2 (en) | 2000-03-13 | 2010-11-10 | テクノポリマー株式会社 | Resin composition for molding vehicle lamp and vehicle lamp using the same |
JP2001302899A (en) | 2000-04-19 | 2001-10-31 | Mitsubishi Rayon Co Ltd | Aromatic polycarbonate resin composition and its molded product |
JP2002020572A (en) | 2000-07-10 | 2002-01-23 | Denki Kagaku Kogyo Kk | Thermoplastic resin composition and its molding |
JP2002133916A (en) | 2000-10-26 | 2002-05-10 | Nippon A & L Kk | Material for lamp housing of lighting apparatus for vehicle |
JP2002161184A (en) | 2000-11-27 | 2002-06-04 | Nippon A & L Kk | Thermoplastic resin material for car light appliance and lamp housing for car light appliance consisting of the same |
JP2003026890A (en) | 2001-07-16 | 2003-01-29 | Nippon A & L Kk | Thermoplastic resin composition |
JP2003055522A (en) | 2001-08-21 | 2003-02-26 | Nippon A & L Kk | Thermoplastic resin composition |
-
2002
- 2002-08-07 CN CN2005100886884A patent/CN1733964B/en not_active Expired - Fee Related
- 2002-08-07 US US10/485,117 patent/US20040249069A1/en not_active Abandoned
-
2010
- 2010-03-03 US US12/716,646 patent/US7910028B2/en not_active Expired - Fee Related
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4894415A (en) * | 1986-09-11 | 1990-01-16 | Mitsubishi Rayon Co., Ltd. | Polyphenylene ether resin composition |
US5043405A (en) * | 1988-01-07 | 1991-08-27 | Asahi Kasei Kogyo Kabushiki Kaisha | Methacrylic copolymer having low moisture absorption properties |
US5391648A (en) * | 1990-07-24 | 1995-02-21 | Mitsubishi Rayon Co., Ltd. | Polyorganosiloxane graft copolymers |
US5132191A (en) * | 1990-10-26 | 1992-07-21 | General Electric Company | Polymer surfaces for subsequent plating thereon and improved metal-plated plastic articles made therefrom |
US5498440A (en) * | 1992-01-21 | 1996-03-12 | General Electric Company | Adhesion of electroless coating to resinous articles |
US5275882A (en) * | 1992-02-03 | 1994-01-04 | General Electric Company | Method for improving adhesion of aluminum layers to thermoplastics and article |
US5543460A (en) * | 1992-02-06 | 1996-08-06 | Mitsubishi Rayon Co., Ltd. | Graft copolymer particles their production and compositions comprising them |
US5804655A (en) * | 1995-09-12 | 1998-09-08 | Kaneka Corporation | Silicone-modified acrylic rubber particles, graft copolymer particles of silicone-modified acrylic rubber and thermoplastic resin composition |
US20040063814A1 (en) * | 2001-02-09 | 2004-04-01 | Nobuo Miyatake | Impact modifier for thermoplastic resin and resin composition containing the same |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20050079928A1 (en) * | 2003-10-07 | 2005-04-14 | Bridgestone Sports Co., Ltd. | Rubber composition for golf ball and golf ball |
US7238746B2 (en) * | 2003-10-07 | 2007-07-03 | Bridgestone Sports Co., Ltd. | Rubber composition for golf ball and golf ball |
WO2006052437A1 (en) * | 2004-11-04 | 2006-05-18 | General Electric Company | Method for reducing stringiness of a resinous composition during hot plate welding |
US20090036607A1 (en) * | 2005-03-03 | 2009-02-05 | Mitsubishi Rayon Co., Ltd. | Polymer particle, resin composition containing same, and molded body |
EP2182016A1 (en) * | 2007-07-13 | 2010-05-05 | Mitsubishi Rayon Co. Ltd. | Graft copolymer, thermoplastic resin composition, and molded object |
US20100187965A1 (en) * | 2007-07-13 | 2010-07-29 | Mitsubishi Rayon Co., Ltd. | Graft copolymer, thermoplastic resin composition and molded product |
EP2182016A4 (en) * | 2007-07-13 | 2010-09-29 | Mitsubishi Rayon Co | Graft copolymer, thermoplastic resin composition, and molded object |
US8569415B2 (en) | 2007-07-13 | 2013-10-29 | Mitsubishi Rayon Co., Ltd. | Graft copolymer, thermoplastic resin composition and molded product |
US8691915B2 (en) | 2012-04-23 | 2014-04-08 | Sabic Innovative Plastics Ip B.V. | Copolymers and polymer blends having improved refractive indices |
EP3369755A4 (en) * | 2015-10-28 | 2019-10-23 | UMG ABS, Ltd. | Graft copolymer, crosslinked particles, graft crosslinked particles, rubbery polymer and thermoplastic resin composition using same |
US11161974B2 (en) * | 2017-06-06 | 2021-11-02 | Mitsubishi Chemical Corporation | Polyorganosiloxane-containing graft copolymer, thermoplastic resin composition, and molded article |
Also Published As
Publication number | Publication date |
---|---|
US7910028B2 (en) | 2011-03-22 |
US20100159134A1 (en) | 2010-06-24 |
CN1733964B (en) | 2011-06-15 |
CN1733964A (en) | 2006-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US7910028B2 (en) | Resin composition for direct vapor deposition, molded articles made by using the same, and surface-metallized lamp housing | |
JP3634964B2 (en) | Graft copolymer particles and thermoplastic resin composition | |
US9328186B2 (en) | Thermoplastic resin composition for vehicle lamp housings | |
JP4907814B2 (en) | Graft copolymer and thermoplastic resin composition containing the same | |
EP1369455B1 (en) | Graft copolymer and thermoplastic resin composition | |
JP4567872B2 (en) | Thermoplastic resin composition | |
JP2005307180A (en) | Thermoplastic resin composition | |
JP3913098B2 (en) | Resin composition and molded article using the same | |
JP5352085B2 (en) | Thermoplastic resin composition for lamp housing and molded product thereof | |
JPH08239544A (en) | Thermoplastic resin composition | |
EP1445281B1 (en) | Resin composition for direct vapor deposition molded articles made by using the same and surface metallized lamp housing | |
JP3875908B2 (en) | Molded product | |
JP4060102B2 (en) | Thermoplastic resin composition | |
JP4285856B2 (en) | Thermoplastic resin composition containing graft copolymer | |
JP6276116B2 (en) | Thermoplastic resin composition and vehicle lamp housing using the same | |
JP2016125006A (en) | Powder containing composite rubber-based graft copolymer, coagulation containing composite rubber-based graft copolymer, thermoplastic resin composition and molded article thereof | |
JP2001158845A (en) | Flame retardant resin composition | |
JP4060111B2 (en) | Thermoplastic resin composition | |
JP2005343925A (en) | Thermoplastic resin composition and molded article using the same | |
JP2958059B2 (en) | Thermoplastic resin composition | |
JP2003160624A (en) | Graft copolymer and thermoplastic resin composition containing the same | |
JP2001261755A (en) | Graft copolymer and thermoplastic resin composition comprising the same | |
JP3467199B2 (en) | Thermoplastic resin composition | |
JPH08239531A (en) | Thermoplastic resin composition | |
CN109415556B (en) | Polycarbonate resin composition and molded article thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: MITSUBISHI RAYON CO., LTD., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:NAKAI, YOSHIHIRO;IKEBE, TAKAHIRO;OBATA, KEIJI;AND OTHERS;REEL/FRAME:015283/0419 Effective date: 20040121 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |