TWI708812B - Resin composition, its manufacturing method, and its molded body - Google Patents
Resin composition, its manufacturing method, and its molded body Download PDFInfo
- Publication number
- TWI708812B TWI708812B TW105116833A TW105116833A TWI708812B TW I708812 B TWI708812 B TW I708812B TW 105116833 A TW105116833 A TW 105116833A TW 105116833 A TW105116833 A TW 105116833A TW I708812 B TWI708812 B TW I708812B
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- Prior art keywords
- mass
- rubber
- resin composition
- graft polymer
- parts
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 196
- 238000004519 manufacturing process Methods 0.000 title claims description 45
- 229920001971 elastomer Polymers 0.000 claims abstract description 234
- 239000005060 rubber Substances 0.000 claims abstract description 231
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 211
- 239000002253 acid Substances 0.000 claims abstract description 168
- 150000003839 salts Chemical class 0.000 claims abstract description 158
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 154
- 239000011575 calcium Substances 0.000 claims abstract description 154
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 154
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 139
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 139
- 239000011777 magnesium Substances 0.000 claims abstract description 139
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 100
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000011521 glass Substances 0.000 claims abstract description 85
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 74
- 239000000194 fatty acid Substances 0.000 claims abstract description 74
- 229930195729 fatty acid Natural products 0.000 claims abstract description 74
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 70
- 125000003118 aryl group Chemical group 0.000 claims abstract description 46
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 44
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 39
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 39
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 30
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000465 moulding Methods 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims description 68
- 229920000126 latex Polymers 0.000 claims description 49
- -1 acrylic compound Chemical class 0.000 claims description 47
- 239000004816 latex Substances 0.000 claims description 46
- 239000003365 glass fiber Substances 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 26
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 25
- 239000006228 supernatant Substances 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 claims description 21
- 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 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- 238000010559 graft polymerization reaction Methods 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 14
- 239000007921 spray Substances 0.000 claims description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000000691 measurement method Methods 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 10
- 239000000284 extract Substances 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 159000000003 magnesium salts Chemical class 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- 239000000701 coagulant Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims 3
- 238000001704 evaporation Methods 0.000 claims 1
- 230000008020 evaporation Effects 0.000 claims 1
- 239000000945 filler Substances 0.000 abstract description 78
- 229920006351 engineering plastic Polymers 0.000 abstract description 65
- 230000000052 comparative effect Effects 0.000 description 46
- 239000000523 sample Substances 0.000 description 44
- 238000005259 measurement Methods 0.000 description 33
- 238000000034 method Methods 0.000 description 31
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000003995 emulsifying agent Substances 0.000 description 26
- 238000005452 bending Methods 0.000 description 24
- 239000007788 liquid Substances 0.000 description 24
- 239000000843 powder Substances 0.000 description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 235000021355 Stearic acid Nutrition 0.000 description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 15
- 239000008117 stearic acid Substances 0.000 description 15
- 238000009863 impact test Methods 0.000 description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 10
- 150000001342 alkaline earth metals Chemical class 0.000 description 10
- 229920000515 polycarbonate Polymers 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000004364 calculation method Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 7
- 238000006460 hydrolysis reaction Methods 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 6
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- 239000005642 Oleic acid Substances 0.000 description 6
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 6
- 235000021314 Palmitic acid Nutrition 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 6
- 239000008116 calcium stearate Substances 0.000 description 6
- 235000013539 calcium stearate Nutrition 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 6
- 235000021313 oleic acid Nutrition 0.000 description 6
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 5
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 5
- 230000015271 coagulation Effects 0.000 description 5
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- 150000002500 ions Chemical class 0.000 description 5
- 229910001425 magnesium ion Inorganic materials 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004420 Iupilon Substances 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 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 4
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 4
- 239000001639 calcium acetate Substances 0.000 description 4
- 229960005147 calcium acetate Drugs 0.000 description 4
- 235000011092 calcium acetate Nutrition 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- 238000005185 salting out Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 4
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 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 3
- 239000012298 atmosphere Substances 0.000 description 3
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 3
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- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
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- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 3
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- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
一種樹脂組成物,其包含工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C),該樹脂組成物的氯仿可溶部分中的源自丙烯腈的成分的比例為2.0質量%以下,該樹脂組成物100質量份中的脂肪酸的含量為0.03質量份以下,藉由氯仿所萃取的樹脂組成物的乾燥試樣100質量份中的鈣及鎂的合計含量為0.0008質量份以下,鋁的含量為0.0008質量份以下。進而,一種樹脂組成物,其含有鹼金屬與強酸的鹽(D)。工程塑膠(A)較佳為芳香族聚碳酸酯樹脂。一種成形體,其是使該樹脂組成物成形而成。 A resin composition comprising an engineering plastic (A), a glass filler (B), and a graft polymer (C) containing rubber, and the proportion of the acrylonitrile-derived component in the chloroform-soluble part of the resin composition 2.0% by mass or less, the content of fatty acids in 100 parts by mass of the resin composition is 0.03 parts by mass or less, and the total content of calcium and magnesium in 100 parts by mass of the dry sample of the resin composition extracted by chloroform is 0.0008 Parts by mass or less, and the content of aluminum is 0.0008 parts by mass or less. Furthermore, a resin composition containing a salt (D) of an alkali metal and a strong acid. The engineering plastic (A) is preferably an aromatic polycarbonate resin. A molded body obtained by molding the resin composition.
Description
本發明是有關於一種包含工程塑膠、玻璃填充劑及含有橡膠的接枝聚合體的樹脂組成物,及使該樹脂組成物成形而成的成形體。 The present invention relates to a resin composition containing engineering plastic, glass filler, and graft polymer containing rubber, and a molded body formed by molding the resin composition.
工程塑膠因其優異的耐熱性而用於汽車構件或家電構件。近年來,以汽車構件、家電構件為中心,輕量化、薄壁化的要求高,於工程塑膠中調配玻璃填充劑(玻璃纖維等)而成的材料因以彎曲強度為代表的剛性得到改良,故可適宜地使用。 Engineering plastics are used for automotive components or home appliance components due to their excellent heat resistance. In recent years, with automotive components and home appliance components as the center, the requirements for lighter weight and thinner walls are high. Materials made by blending glass fillers (glass fibers, etc.) into engineering plastics have been improved due to their rigidity represented by bending strength. Therefore, it can be used appropriately.
該些材料的玻璃填充劑與工程塑膠的密接性越良好,剛性或耐熱性等的改良效果越大。但是,耐衝擊性、特別是缺口強度(notched strength)因玻璃填充劑的調配而下降。因此,以衝擊強度的改善為目的而考慮於該些材料中調配含有橡膠的接枝聚合體,但若調配先前所揭示的含有橡膠的接枝聚合體,則會對玻璃填充劑與工程塑膠的密接性帶來不良影響。 The better the adhesion between the glass filler of these materials and the engineering plastic, the greater the effect of improving rigidity or heat resistance. However, impact resistance, particularly notched strength (notched strength) is reduced by the blending of the glass filler. Therefore, for the purpose of improving the impact strength, it is considered that the rubber-containing graft polymer is formulated in these materials. However, if the rubber-containing graft polymer disclosed previously is formulated, the glass filler and engineering plastics Adhesion has an adverse effect.
尤其於要求成形體的尺寸穩定性的領域中,於吸水性低的芳香族聚碳酸酯樹脂中調配玻璃填充劑來應對的例子增多。但 是,即便於芳香族聚碳酸酯樹脂與玻璃填充劑中調配先前所揭示的含有橡膠的接枝聚合體,缺口強度的改良效果亦特別少,另一方面,彎曲強度等剛性下降。 Particularly in the field where the dimensional stability of the molded body is required, the number of examples where a glass filler is formulated in an aromatic polycarbonate resin with low water absorption to deal with it has increased. but Yes, even if the rubber-containing graft polymer disclosed previously is blended with an aromatic polycarbonate resin and a glass filler, the effect of improving notch strength is particularly small. On the other hand, rigidity such as bending strength decreases.
含有橡膠的接枝聚合體通常藉由乳化聚合來製造,並藉由鈣系、鎂系或鋁系的鹽或酸來回收而獲得。於回收工程塑膠用含有橡膠的接枝聚合體時,使用鈣系、鎂系或鋁系的鹽的情況多。但是,當存在源自含有橡膠的接枝聚合體的鈣及鎂與強酸的鹽、以及鋁與強酸的鹽時,玻璃填充劑與樹脂的密接性下降。 The rubber-containing graft polymer is usually produced by emulsion polymerization, and is obtained by recycling calcium, magnesium, or aluminum salts or acids. When recycling rubber-containing graft polymers for engineering plastics, calcium-based, magnesium-based, or aluminum-based salts are often used. However, when the salt of calcium and magnesium derived from a graft polymer containing rubber and a strong acid and a salt of aluminum and a strong acid are present, the adhesion between the glass filler and the resin decreases.
於專利文獻1中揭示有如下的例子:於工程塑膠與玻璃填充劑中調配10質量份左右的考慮利用鈣系的鹽進行鹽析的含有橡膠的接枝聚合體(包含多於1000ppm的鈣)。 The following example is disclosed in Patent Document 1: a rubber-containing graft polymer (containing more than 1000 ppm of calcium) prepared with about 10 parts by mass of engineering plastics and glass fillers considering the use of calcium-based salts for salting out .
含有橡膠的接枝聚合體亦可將脂肪酸系的鹼金屬鹽作為乳化劑來進行乳化聚合。因此,可藉由酸凝固而非鹽析來回收含有橡膠的接枝聚合體。脂肪酸系的乳化劑藉由酸而變化成脂肪酸且親水性下降,因此乳膠中的含有橡膠的接枝聚合體凝聚。對其進行脫水、清洗、乾燥,而可作為含有橡膠的接枝聚合體的粉體進行回收。於專利文獻2中揭示有如下的例子:於芳香族聚碳酸酯樹脂與玻璃填充劑中調配含有橡膠的接枝聚合體的粉體,該含有橡膠的接枝聚合體的粉體是藉由酸來回收包含利用脂肪酸系乳化劑所製造的含有橡膠的接枝聚合體的乳膠而成。但是,脂肪酸亦會使玻璃與樹脂的密接性下降。 The rubber-containing graft polymer may be emulsified and polymerized using an alkali metal salt of a fatty acid system as an emulsifier. Therefore, the graft polymer containing rubber can be recovered by acid coagulation instead of salting out. The fatty acid-based emulsifier is changed into fatty acid by acid and its hydrophilicity is reduced, so the rubber-containing graft polymer in the latex aggregates. It is dehydrated, washed, and dried, and can be recovered as a powder of a graft polymer containing rubber. Patent Document 2 discloses the following example: an aromatic polycarbonate resin and a glass filler are mixed with a rubber-containing graft polymer powder, and the rubber-containing graft polymer powder is prepared by acid To recover the latex containing the rubber-containing graft polymer produced by the fatty acid-based emulsifier. However, fatty acids also reduce the adhesion between glass and resin.
[現有技術文獻] [Prior Art Literature]
[專利文獻] [Patent Literature]
[專利文獻1]日本專利特表2004-514782號公報 [Patent Document 1] Japanese Patent Publication No. 2004-514782
[專利文獻2]日本專利特開2007-211157號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2007-211157
本發明者等人進行研究的結果,發現以不含使玻璃填充劑與樹脂的密接性下降的鈣及鎂與強酸的鹽、鋁與強酸的鹽或脂肪酸的方式製造含有橡膠的接枝聚合體,並將其調配至工程塑膠與玻璃填充劑的樹脂組成物中,藉此可不使玻璃填充劑與樹脂的密接性下降,而將橡膠調配至樹脂中,且可不使成形體的剛性、特別是彎曲強度及斷裂伸長率下降,而顯現查皮衝擊強度(charpy impact strength)等機械強度。 As a result of research conducted by the inventors, it was found that a graft polymer containing rubber is produced without containing calcium and magnesium salts with strong acids, aluminum with strong acids or fatty acids, which reduce the adhesion between the glass filler and resin , And blending it into the resin composition of engineering plastics and glass fillers, so that the rubber can be blended into the resin without reducing the adhesion between the glass filler and the resin, and the rigidity of the molded body, especially Bending strength and elongation at break decrease, and mechanical strength such as charpy impact strength appears.
所述課題藉由以下的本發明[1]~[19]的任一者來解決。 The problem is solved by any one of the following inventions [1] to [19].
[1]一種樹脂組成物,其包含工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C),該樹脂組成物的氯仿可溶部分中的源自丙烯腈的成分的比例為2.0質量%以下,該樹脂組成物100質量份中的脂肪酸的含量為0.03質量份以下,藉由下述的測定方法X所測定的乾燥試樣100質量份中的鈣及鎂的合計含量為0.0008質量份以下,鋁的含量為0.0008質量份以下。 [1] A resin composition comprising an engineering plastic (A), a glass filler (B), and a rubber-containing graft polymer (C), the chloroform-soluble part of the resin composition is derived from acrylonitrile The ratio of components is 2.0% by mass or less, the content of fatty acids in 100 parts by mass of the resin composition is 0.03 parts by mass or less, and the content of calcium and magnesium in 100 parts by mass of a dry sample measured by the following measuring method X The total content is 0.0008 parts by mass or less, and the aluminum content is 0.0008 parts by mass or less.
[測定方法X]: [Measurement Method X]:
<1>乾燥試樣的製備 <1> Preparation of dry samples
製備包含樹脂組成物5質量%及氯仿95質量%的溶液,並進行以下(1)~(4)的操作,而獲得「乾燥試樣」。 A solution containing 5% by mass of the resin composition and 95% by mass of chloroform was prepared, and the following operations (1) to (4) were performed to obtain a "dry sample".
(1)將所述溶液供於離心分離機並以5000rpm進行30分鐘離心分離。 (1) The solution is supplied to a centrifuge and centrifuged at 5000 rpm for 30 minutes.
(2)對上清液進行萃取,並放入至燒瓶內。 (2) Extract the supernatant and put it into the flask.
(3)將該燒瓶設置於溫度為68℃的恆溫槽中,並利用蒸發器自該上清液中餾去揮發成分。 (3) The flask was set in a constant temperature bath at a temperature of 68°C, and volatile components were distilled off from the supernatant with an evaporator.
(4)於溫度120℃下對該燒瓶內的殘存物進行3小時乾燥而獲得「乾燥試樣」。 (4) Dry the residue in the flask at a temperature of 120°C for 3 hours to obtain a "dry sample".
<2>對所述乾燥試樣中的鋁、鎂及鈣進行定量。 <2> Quantify aluminum, magnesium, and calcium in the dried sample.
[2]如所述[1]的樹脂組成物,其中所述鈣及鎂的合計含量為0.0006質量份以下。 [2] The resin composition according to [1], wherein the total content of calcium and magnesium is 0.0006 parts by mass or less.
[3]一種樹脂組成物,其包含工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C),含有橡膠的接枝聚合體(C)的丙酮不溶部分為25質量%以上,含有橡膠的接枝聚合體(C)中所含的脂肪酸的含量為1質量%以下,相對於工程塑膠(A)、玻璃填充劑(B)、及含有橡膠的接枝聚合體(C)的合計100質量份,該樹脂組成物中的鈣或鎂與強酸的鹽的合計含量的鈣及鎂換算的合計含量為0.0008質量份以下,鋁與強酸的鹽的含量的鋁換算的含量為0.0008質量份以下。 [3] A resin composition comprising an engineering plastic (A), a glass filler (B), and a rubber-containing graft polymer (C), and the rubber-containing graft polymer (C) has an acetone-insoluble part of 25 Mass% or more, the content of fatty acid contained in the rubber-containing graft polymer (C) is 1% by mass or less, relative to engineering plastic (A), glass filler (B), and rubber-containing graft polymer The total content of (C) is 100 parts by mass, the total content of calcium or magnesium in the resin composition in terms of calcium and magnesium is 0.0008 parts by mass or less, and the content of aluminum and the salt of strong acid is calculated as aluminum The content is 0.0008 parts by mass or less.
[4]如所述[3]的樹脂組成物,其中所述鈣及鎂換算的合計含量為0.0006質量份以下。 [4] The resin composition according to the above [3], wherein the total content in terms of calcium and magnesium is 0.0006 parts by mass or less.
[5]如所述[1]至[4]中任一項的樹脂組成物,其更含有鹼金屬與強酸的鹽(D)。 [5] The resin composition according to any one of [1] to [4], which further contains a salt (D) of an alkali metal and a strong acid.
[6]如所述[5]的樹脂組成物,其中所述樹脂組成物100質量份中的所述鹼金屬與強酸的鹽(D)的含量為0.01質量份~0.5質量份。 [6] The resin composition according to [5], wherein the content of the alkali metal and strong acid salt (D) in 100 parts by mass of the resin composition is 0.01 to 0.5 parts by mass.
[7]如所述[1]至[6]中任一項的樹脂組成物,其中所述含有橡膠的接枝聚合體(C)是使用凝聚劑(coagulating agent)對含有橡膠的接枝聚合體乳膠進行凝聚回收或進行噴霧回收所獲得者,所述含有橡膠的接枝聚合體乳膠是在包含鹼金屬與強酸的鹽(D)的橡膠乳膠的存在下,使乙烯基單量體進行乳化聚合而獲得。 [7] The resin composition according to any one of [1] to [6], wherein the rubber-containing graft polymer (C) is graft-polymerized using a coagulating agent to the rubber Body latex is obtained by coagulation recovery or spray recovery. The rubber-containing graft polymer latex is obtained by emulsifying vinyl monomer in the presence of rubber latex containing alkali metal and strong acid salt (D) Obtained by polymerization.
[8]如所述[1]至[7]中任一項的樹脂組成物,其中所述含有橡膠的接枝聚合體(C)是進行噴霧回收所獲得者。 [8] The resin composition according to any one of [1] to [7], wherein the rubber-containing graft polymer (C) is obtained by spray recovery.
[9]如所述[1]至[8]中任一項的樹脂組成物,其中於所述樹脂組成物中,相對於工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的合計100質量份,以鈣及鎂換算的合計量計進而含有0.0010質量份~0.0060質量份的源自玻璃填充劑(B)以外的成分的鈣或鎂與弱酸的鹽。 [9] The resin composition according to any one of [1] to [8], wherein in the resin composition, the engineering plastic (A), the glass filler (B), and the rubber-containing adhesive A total of 100 parts by mass of the branch polymer (C), in terms of the total amount of calcium and magnesium, further contains 0.0010 parts to 0.0060 parts by mass of calcium or magnesium and a weak acid salt derived from components other than the glass filler (B) .
[10]如所述[1]至[9]中任一項的樹脂組成物,其中所述含有橡膠的接枝聚合體(C)中的橡膠狀聚合體的質量平均粒徑為300nm以下。 [10] The resin composition according to any one of [1] to [9], wherein the rubber-like polymer in the rubber-containing graft polymer (C) has a mass average particle diameter of 300 nm or less.
[11]如所述[1]至[10]中任一項的樹脂組成物,其中所述工程塑膠(A)為芳香族聚碳酸酯樹脂。 [11] The resin composition according to any one of [1] to [10], wherein the engineering plastic (A) is an aromatic polycarbonate resin.
[12]如所述[5]至[11]中任一項記載的樹脂組成物,其中所述鹼金屬與強酸的鹽(D)為鈉或鉀與磺酸的鹽。 [12] The resin composition according to any one of [5] to [11], wherein the salt of alkali metal and strong acid (D) is a salt of sodium or potassium and sulfonic acid.
[13]如所述[1]至[12]中任一項的樹脂組成物,其中於工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的合計100質量%中,所述含有橡膠的接枝聚合體(C)的含量為0.25質量%~15質量%。 [13] The resin composition according to any one of [1] to [12], wherein the total amount of engineering plastic (A), glass filler (B), and rubber-containing graft polymer (C) is 100 In mass %, the content of the rubber-containing graft polymer (C) is 0.25% to 15% by mass.
[14]如所述[1]至[12]中任一項的樹脂組成物,其中於工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的合計100質量%中,所述含有橡膠的接枝聚合體(C)的含量為0.25質量%~7.5質量%。 [14] The resin composition according to any one of [1] to [12], wherein the total amount of engineering plastic (A), glass filler (B), and rubber-containing graft polymer (C) is 100 In mass %, the content of the rubber-containing graft polymer (C) is 0.25% to 7.5% by mass.
[15]如所述[1]至[14]中任一項的樹脂組成物,其中於工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的合計100質量%中,所述玻璃填充劑(B)的含量為5質量%~40質量%。 [15] The resin composition according to any one of [1] to [14], wherein the total amount of engineering plastic (A), glass filler (B), and rubber-containing graft polymer (C) is 100 In mass %, the content of the glass filler (B) is 5 mass% to 40 mass %.
[16]如所述[1]至[15]中任一項的樹脂組成物,其中所述含有橡膠的接枝聚合體(C)包含選自丁二烯橡膠、苯乙烯.丁二烯共聚橡膠及矽酮.丙烯酸複合橡膠中的一種以上的橡膠。 [16] The resin composition according to any one of [1] to [15], wherein the rubber-containing graft polymer (C) comprises a butadiene rubber and styrene. Butadiene copolymer rubber and silicone. More than one type of rubber in acrylic compound rubber.
[17]如所述[1]至[16]中任一項的樹脂組成物,其中所述玻璃填充劑(B)為玻璃纖維。 [17] The resin composition according to any one of [1] to [16], wherein the glass filler (B) is glass fiber.
[18]一種成形體,其是使如所述[1]至[17]中任一項的樹脂組成物成形而成。 [18] A molded body obtained by molding the resin composition as described in any one of [1] to [17].
[19]一種製造樹脂組成物的方法,其將工程塑膠(A),玻璃 填充劑(B),以及丙酮不溶部分為25質量%以上且脂肪酸的含量為1質量%以下的含有橡膠的接枝聚合體(C)混合,並且相對於工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的合計100質量份,源自含有橡膠的接枝聚合體(C)的鈣或鎂與強酸的鹽的合計含量以鈣及鎂換算的合計含量計為0.0008質量份以下,源自含有橡膠的接枝聚合體(C)的鋁與強酸的鹽的含量以鋁換算的含量計為0.0008質量份以下。 [19] A method of manufacturing a resin composition that combines engineering plastics (A), glass The filler (B) and the rubber-containing graft polymer (C) whose acetone-insoluble part is 25% by mass or more and the fatty acid content is 1% by mass or less are mixed, and compared to engineering plastics (A) and glass fillers ( B) and a total of 100 parts by mass of the rubber-containing graft polymer (C), the total content of the salt of calcium or magnesium and the strong acid derived from the rubber-containing graft polymer (C) is the total content in terms of calcium and magnesium It is 0.0008 parts by mass or less, and the content of the salt of aluminum and strong acid derived from the rubber-containing graft polymer (C) is 0.0008 parts by mass or less in terms of aluminum.
根據本發明,可提昇先前困難的樹脂與玻璃填充劑的密接性,並將橡膠分散於樹脂中來改良成形體的機械物性。 According to the present invention, it is possible to improve the adhesion between the previously difficult resin and the glass filler, and to disperse rubber in the resin to improve the mechanical properties of the molded body.
圖1是實施例3的成形體的查皮衝擊試驗後的斷裂面。 FIG. 1 shows the fracture surface of the molded body of Example 3 after the skin impact test.
圖2是比較例4的成形體的查皮衝擊試驗後的斷裂面。 Fig. 2 is a fracture surface of a molded body of Comparative Example 4 after a skin impact test.
圖3是實施例4的成形體的查皮衝擊試驗後的斷裂面。 Fig. 3 is a fracture surface of the molded body of Example 4 after a skin impact test.
圖4是比較例1的成形體的查皮衝擊試驗後的斷裂面。 Fig. 4 is a fracture surface of a molded body of Comparative Example 1 after a skin impact test.
圖5是比較例2的成形體的查皮衝擊試驗後的斷裂面。 Fig. 5 is a fracture surface of a molded body of Comparative Example 2 after a skin impact test.
圖6是比較例3的成形體的查皮衝擊試驗後的斷裂面。 Fig. 6 is a fracture surface of a molded body of Comparative Example 3 after a skin impact test.
圖7是比較例5的成形體的查皮衝擊試驗後的斷裂面。 FIG. 7 shows the fracture surface of the molded body of Comparative Example 5 after the skin impact test.
[工程塑膠(A)] [Engineering Plastics (A)]
於本發明的樹脂組成物中,作為工程塑膠(A),可使用先前 已知的各種熱塑性工程塑膠。於本發明中,所謂「工程塑膠」,是指於0.45MPa的負荷下,藉由依據ISO-75的方法所測定的熱變形溫度(Heat Deflection Temperature,HDT)為100℃以上者。例如可例示:聚苯醚,聚碳酸酯、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等聚酯系聚合體,間規聚苯乙烯,6-尼龍、6,6-尼龍等尼龍系聚合體,聚芳酯,聚苯硫醚,聚醚酮,聚醚醚酮,聚碸,聚醚碸,聚醯胺醯亞胺,聚醚醯亞胺,聚縮醛。 In the resin composition of the present invention, as the engineering plastic (A), the previous Various known thermoplastic engineering plastics. In the present invention, the so-called "engineering plastics" refers to those having a heat deflection temperature (HDT) of 100°C or higher as measured by a method according to ISO-75 under a load of 0.45 MPa. For example, polyphenylene ether, polycarbonate, polyethylene terephthalate, polybutylene terephthalate and other polyester polymers, syndiotactic polystyrene, 6-nylon, 6,6- Nylon-based polymers such as nylon, polyarylate, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether, polyether, polyimide, polyetherimide, polyacetal.
另外,作為本發明的工程塑膠(A),亦可例示顯示出所述熱變形溫度(HDT),且耐熱性優異、具有熔融流動性的耐熱丙烯腈-丁二烯-苯乙烯(Acrylonitrile Butadiene Styrene,ABS)等特殊的苯乙烯系樹脂或耐熱丙烯酸系樹脂等。該些之中,就耐熱性與薄壁尺寸穩定性這一點而言,較佳為聚苯醚樹脂、聚碳酸酯樹脂等,更佳為芳香族聚碳酸酯樹脂。另外,該些可單獨使用、或將兩種以上組合使用。 In addition, as the engineering plastic (A) of the present invention, a heat-resistant Acrylonitrile Butadiene Styrene (Acrylonitrile Butadiene Styrene) which exhibits the heat distortion temperature (HDT), is excellent in heat resistance and has melt fluidity, can also be exemplified. , ABS) and other special styrene resins or heat-resistant acrylic resins. Among these, in terms of heat resistance and thin-wall dimensional stability, polyphenylene ether resin, polycarbonate resin, etc. are preferred, and aromatic polycarbonate resin is more preferred. In addition, these can be used alone or in combination of two or more kinds.
作為芳香族聚碳酸酯樹脂,可列舉:4,4'-二羥基二苯基-2,2-丙烷(即雙酚A)系聚碳酸酯等4,4'-二氧基二芳基烷烴系聚碳酸酯。 Examples of aromatic polycarbonate resins include 4,4'-dioxydiarylalkanes such as 4,4'-dihydroxydiphenyl-2,2-propane (ie bisphenol A) polycarbonate It is polycarbonate.
所述工程塑膠(A)的分子量可對應於期望而適宜設定,並無特別限制。但是,當工程塑膠(A)為芳香族聚碳酸酯樹脂時,若黏度平均分子量為15000~30000,則樹脂組成物的成形加工性良好,所獲得的成形體的耐衝擊性良好。若黏度平均分子量為15000以上,則就樹脂組成物的射出成型時的成形體的模具脫模時 的破損少、且所獲得的成形體的衝擊強度良好的觀點而言較佳。若黏度平均分子量為30000以下,則樹脂組成物變成可藉由通常的擠出成型、射出成型來成形的熔融黏度,而較佳。再者,「黏度平均分子量」是藉由根據黏度法或凝膠滲透層析(Gel Permeation Chromatography,GPC)法的黏度換算來算出。 The molecular weight of the engineering plastic (A) can be appropriately set according to expectations, and is not particularly limited. However, when the engineering plastic (A) is an aromatic polycarbonate resin, if the viscosity average molecular weight is 15,000 to 30,000, the molding processability of the resin composition is good, and the resulting molded body has good impact resistance. If the viscosity average molecular weight is 15000 or more, the mold of the molded body during injection molding of the resin composition will be released. It is preferable from the viewpoint of less damage and good impact strength of the obtained molded body. If the viscosity average molecular weight is 30,000 or less, the resin composition has a melt viscosity that can be molded by ordinary extrusion molding or injection molding, which is preferable. In addition, "viscosity average molecular weight" is calculated by viscosity conversion according to the viscosity method or the gel permeation chromatography (Gel Permeation Chromatography, GPC) method.
工程塑膠(A)可藉由公知的方法來製造。例如,當製造4,4'-二羥基二苯基-2,2-丙烷系聚碳酸酯時,可列舉:將4,4'-二羥基二苯基-2,2-丙烷用作原料,於鹼性水溶液及溶劑的存在下吹入光氣來進行反應的方法;或於觸媒的存在下,使4,4'-二羥基二苯基-2,2-丙烷與碳酸二酯進行酯交換的方法。 The engineering plastic (A) can be manufactured by a known method. For example, when manufacturing 4,4'-dihydroxydiphenyl-2,2-propane-based polycarbonate, 4,4'-dihydroxydiphenyl-2,2-propane is used as a raw material, A method in which phosgene is blown into the reaction in the presence of an alkaline aqueous solution and a solvent; or in the presence of a catalyst, 4,4'-dihydroxydiphenyl-2,2-propane is esterified with a carbonic acid diester Exchange method.
[玻璃填充劑(B)] [Glass Filler (B)]
於本發明中,玻璃填充劑(B)是將矽酸鹽作為主成分的物質,可列舉:層狀矽酸鹽,滑石、雲母、二氧化矽等多孔質粒子,玻璃(玻璃纖維、磨碎玻璃、玻璃片、玻璃珠等)等。就成形體的彎曲特性的觀點而言,特佳為玻璃纖維。 In the present invention, the glass filler (B) is a substance containing silicate as the main component, and examples thereof include layered silicate, porous particles such as talc, mica, and silica, and glass (glass fiber, ground Glass, glass flakes, glass beads, etc.) etc. From the viewpoint of the bending characteristics of the molded body, glass fiber is particularly preferred.
[含有橡膠的接枝聚合體(C)] [Graft polymer containing rubber (C)]
構成本發明的樹脂組成物的含有橡膠的接枝聚合體(C)是使「乙烯基系單量體」對於「橡膠狀聚合體」進行接枝聚合而成者。以下,將構成含有橡膠的接枝聚合體(C)的源自接枝聚合的成分稱為「接枝成分」。 The rubber-containing graft polymer (C) constituting the resin composition of the present invention is obtained by graft-polymerizing the "vinyl monomer" to the "rubber polymer". Hereinafter, the component derived from graft polymerization constituting the rubber-containing graft polymer (C) is referred to as "graft component".
作為橡膠狀聚合體,可使用玻璃轉移溫度為0℃以下者。若橡膠狀聚合體的玻璃轉移溫度為0℃以下,則由本發明的樹 脂組成物所獲得的成形體的由查皮衝擊試驗的值所表示的衝擊強度得到改善。作為橡膠狀聚合體,具體而言,可列舉以下者。丁二烯橡膠,苯乙烯.丁二烯共聚橡膠,矽酮橡膠,矽酮.丙烯酸複合橡膠(於由將二甲基矽氧烷作為主體的單量體所獲得的橡膠狀聚合體的存在下,使一種或兩種以上的乙烯基系單量體進行聚合所獲得者),丙烯腈.丁二烯共聚橡膠,聚丙烯酸丁酯等丙烯酸系橡膠,聚異戊二烯,聚氯丁二烯,乙烯.丙烯橡膠,乙烯.丙烯.二烯三元共聚橡膠,苯乙烯.丁二烯嵌段共聚橡膠、苯乙烯.異戊二烯嵌段共聚橡膠等嵌段共聚物,以及該些的氫化物等。因於寒冷地區要求更低的溫度(-20℃以下)下的成形體的衝擊強度的改良,故較佳為玻璃轉移溫度為-20℃以下的丁二烯橡膠、苯乙烯.丁二烯共聚橡膠、矽酮.丙烯酸複合橡膠。 As the rubbery polymer, one having a glass transition temperature of 0°C or less can be used. If the glass transition temperature of the rubber-like polymer is below 0°C, the resin of the present invention The impact strength represented by the value of the skin impact test of the molded body obtained from the grease composition is improved. Specific examples of the rubber-like polymer include the following. Butadiene rubber, styrene. Butadiene copolymer rubber, silicone rubber, silicone. Acrylic composite rubber (obtained by polymerizing one or two or more vinyl monomers in the presence of a rubber-like polymer obtained from a monomer containing dimethylsiloxane as the main body), Acrylonitrile. Butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene. Propylene rubber, ethylene. Propylene. Diene ternary copolymer rubber, styrene. Butadiene block copolymer rubber, styrene. Block copolymers such as isoprene block copolymer rubber, and hydrogenated products of these. Since cold regions require improvement of the impact strength of the molded body at a lower temperature (below -20°C), butadiene rubber and styrene with a glass transition temperature of -20°C or less are preferred. Butadiene copolymer rubber, silicone. Acrylic compound rubber.
橡膠狀聚合體的質量平均粒徑較佳為300nm以下,其原因在於:成形體的衝擊強度優異。橡膠狀聚合體的質量平均粒徑較佳為50nm以上,更佳為70nm~300nm的範圍內,進而更佳為100nm~300nm的範圍內。橡膠狀聚合體的質量平均粒徑藉由毛細管粒度分佈計來測定。作為使質量平均粒徑變成300nm以下的方法,較佳為利用乳化聚合來製造橡膠狀聚合體,藉由調整乳化劑的量,可獲得質量平均粒徑為50nm~300nm的橡膠狀聚合體。 The mass average particle size of the rubber-like polymer is preferably 300 nm or less because the molded body has excellent impact strength. The mass average particle diameter of the rubber-like polymer is preferably 50 nm or more, more preferably in the range of 70 nm to 300 nm, and still more preferably in the range of 100 nm to 300 nm. The mass average particle size of the rubber-like polymer is measured with a capillary particle size distribution meter. As a method for reducing the mass average particle diameter to 300 nm or less, it is preferable to manufacture a rubber-like polymer by emulsion polymerization. By adjusting the amount of the emulsifier, a rubber-like polymer having a mass average particle diameter of 50 nm to 300 nm can be obtained.
作為對於橡膠狀聚合體進行接枝聚合的乙烯基系單量體,例如可列舉:苯乙烯、α-甲基苯乙烯等芳香族乙烯基化合物; 丙烯酸甲酯、丙烯酸丁酯等丙烯酸酯;甲基丙烯酸甲酯、甲基丙烯酸乙酯等甲基丙烯酸酯等。該些單量體可單獨使用一種、或將兩種以上組合使用。就自其後的凝聚步驟所獲得的粉體特性(粉體的流動性或粒徑)的觀點而言,較佳為以使乙烯基系單量體進行聚合(均聚或將兩種以上組合來進行共聚)所獲得的聚合體或共聚物的玻璃轉移溫度變成70℃以上的方式選擇乙烯基系單量體。 Examples of vinyl monomers that are graft-polymerized to the rubber-like polymer include aromatic vinyl compounds such as styrene and α-methylstyrene; Acrylates such as methyl acrylate and butyl acrylate; methacrylates such as methyl methacrylate and ethyl methacrylate. These monomers can be used alone or in combination of two or more. From the viewpoint of the powder characteristics (fluidity or particle size of the powder) obtained from the subsequent coagulation step, it is preferable to polymerize a vinyl monomer (homopolymerization or a combination of two or more Copolymerization) The vinyl monomer is selected so that the glass transition temperature of the obtained polymer or copolymer becomes 70°C or higher.
以所述方式製造的含有橡膠的接枝聚合體(C)的粉體的質量平均粒徑較佳為300μm~500μm。若該粉體的粒徑為300μm以上,則於製備樹脂組成物時的調配時或朝混合裝置內的投入時,可抑制飛散,且無產生粉塵爆炸等不良情況之虞。另外,若該粉體的粒徑為500μm以下,則粉體的流動特性良好,且無產生製造步驟中的配管的堵塞等不良情況之虞。 The mass average particle diameter of the powder of the rubber-containing graft polymer (C) produced in the manner described above is preferably 300 μm to 500 μm. If the particle size of the powder is 300 μm or more, it is possible to suppress scattering when preparing the resin composition or when it is put into a mixing device, and there is no risk of causing problems such as dust explosion. In addition, if the particle size of the powder is 500 μm or less, the flow characteristics of the powder are good, and there is no risk of occurrence of problems such as clogging of piping in the manufacturing process.
包含對於橡膠狀聚合體進行接枝聚合的乙烯基系單量體的聚合體的玻璃轉移溫度更佳為80℃以上,進而更佳為80℃~90℃的範圍內。例如甲基丙烯酸甲酯與丙烯酸丁酯的共聚物、苯乙烯與丙烯腈的共聚物容易將玻璃轉移溫度設定為80℃~90℃的範圍,而可適宜地使用。 The glass transition temperature of the polymer containing the vinyl monomer graft-polymerized to the rubber-like polymer is more preferably 80°C or higher, and still more preferably in the range of 80°C to 90°C. For example, a copolymer of methyl methacrylate and butyl acrylate, and a copolymer of styrene and acrylonitrile can easily set the glass transition temperature to the range of 80°C to 90°C, and can be suitably used.
當進行接枝聚合的乙烯基系單量體為苯乙烯與丙烯腈的單量體混合物時,就接枝聚合的聚合性、或含有橡膠的接枝聚合體(C)對於工程塑膠(A)的相容性的觀點而言,相對於該單量體混合物100質量%的丙烯腈的比率較佳為35質量%以下。該 比率更佳為15質量%~30質量%的範圍內,進而更佳為18質量%~27質量%的範圍內,特佳為20質量%~26質量%的範圍內。 When the vinyl monomer for graft polymerization is a monomer mixture of styrene and acrylonitrile, the polymerizability of graft polymerization or the rubber-containing graft polymer (C) is for engineering plastics (A) From the viewpoint of the compatibility of, the ratio of acrylonitrile relative to 100% by mass of the monomer mixture is preferably 35% by mass or less. The The ratio is more preferably in the range of 15% by mass to 30% by mass, still more preferably in the range of 18% by mass to 27% by mass, and particularly preferably in the range of 20% by mass to 26% by mass.
於供於接枝聚合的乙烯基系單量體中,存在實際上與橡膠狀聚合體進行化學鍵結的「乙烯基系單量體mgp」;不與橡膠狀聚合體進行化學鍵結,進行聚合而生成「游離聚合體Pfr」的「乙烯基系單量體mfp」;以及不進行聚合反應的「乙烯基系單量體mfm」。該些之中,較佳為與橡膠狀聚合體進行化學鍵結的乙烯基系單量體mgp的量多。若與橡膠狀聚合體進行化學鍵結的乙烯基系單量體的量多,則含有橡膠的接枝聚合體(C)容易分散於工程塑膠(A)中,另外,工程塑膠(A)與含有橡膠的接枝聚合體(C)的界面強度提昇。含有橡膠的接枝聚合體(C)的分散性越良好且界面強度越強,成形體的衝擊強度越提昇,故較佳。不進行聚合反應的乙烯基系單量體mfm於其後的回收步驟(凝固或噴霧回收步驟與所獲得的粉體的乾燥步驟)中,大致全部被去除。 Among the vinyl monomers used for graft polymerization, there is a "vinyl monomer m gp " that actually chemically bonds with the rubber-like polymer; it does not chemically bond with the rubber-like polymer to polymerize The "vinyl monomer m fp "of the "free polymer P fr "; and the "vinyl monomer m fm " that does not undergo polymerization. Among these, it is preferable that the amount of the vinyl monomer m gp chemically bonded to the rubber-like polymer is large. If the amount of vinyl monomer chemically bonded to the rubber-like polymer is large, the rubber-containing graft polymer (C) is easily dispersed in the engineering plastic (A). In addition, the engineering plastic (A) and the The interface strength of the rubber graft polymer (C) is improved. The better the dispersibility of the rubber-containing graft polymer (C) and the stronger the interfacial strength, the better the impact strength of the molded body is improved. The vinyl monomer m fm that does not undergo polymerization is almost completely removed in the subsequent recovery step (solidification or spray recovery step and drying step of the obtained powder).
因由所述乙烯基系單量體mgp形成含有橡膠的接枝聚合體(C)的「接枝成分」,由所述乙烯基系單量體mfp生成「游離聚合體Pfr」(以下,有時稱為「非接枝成分」),故於作為粉體集合物所回收的含有橡膠的接枝聚合體(C)中,混合存在有該「游離聚合體Pfr」。因此,於本發明中,含有橡膠的接枝聚合體(C)是由下式所表示的包含三成分的成分。WC=Wrp+Wgc+Pfr‧‧‧(1) Since the vinyl monomer m gp forms the "graft component" of the rubber-containing graft polymer (C), the vinyl monomer m fp generates "free polymer P fr " (hereinafter , Sometimes referred to as "non-grafted component"), so the "free polymer P fr "is mixed in the rubber-containing graft polymer (C) recovered as a powder aggregate. Therefore, in the present invention, the rubber-containing graft polymer (C) is a three-component component represented by the following formula. WC=W rp +W gc +P fr ‧‧‧(1)
WC:含有橡膠的接枝聚合體(C)的質量 WC: mass of graft polymer (C) containing rubber
Wrp:橡膠狀聚合體的質量 W rp : the quality of the rubber-like polymer
Wgc:接枝成分的質量 W gc : the quality of the grafted ingredients
Pfr:游離聚合體。 P fr : free polymer.
含有橡膠的接枝聚合體(C)中的源自與橡膠狀聚合體進行化學鍵結的乙烯基系單量體的構成單元的比例可作為自含有橡膠的接枝聚合體(C)的丙酮不溶部分中減去橡膠狀聚合體的質量所得的量來進行定量。就此種觀點而言,丙酮不溶部分較佳為25質量%以上,更佳為50質量%以上,進而更佳為83質量%以上,特佳為95質量%以上。 The ratio of the structural unit derived from the vinyl monomer chemically bonded to the rubber-like polymer in the rubber-containing graft polymer (C) can be regarded as insoluble in acetone from the rubber-containing graft polymer (C) The amount obtained by subtracting the mass of the rubber-like polymer from the part was quantified. From this viewpoint, the acetone-insoluble portion is preferably 25% by mass or more, more preferably 50% by mass or more, still more preferably 83% by mass or more, particularly preferably 95% by mass or more.
丙酮不溶部分是藉由製備包含含有橡膠的接枝聚合體1質量%與丙酮99質量%的溶液,並進行以下(1)~(4)的操作來測定。 The acetone-insoluble part was measured by preparing a solution containing 1% by mass of a rubber-containing graft polymer and 99% by mass of acetone, and performing the following operations (1) to (4).
(1)將所述溶液供於離心分離機並以20000rpm進行30分鐘離心分離。 (1) The solution was supplied to a centrifuge and centrifuged at 20000 rpm for 30 minutes.
(2)對上清液進行萃取,並放入至燒瓶內。 (2) Extract the supernatant and put it into the flask.
(3)將該燒瓶設置於溫度為56℃的恆溫槽中,並利用蒸發器自該上清液中餾去揮發成分。 (3) The flask was set in a constant temperature bath at a temperature of 56°C, and volatile components were distilled off from the supernatant by an evaporator.
(4)於溫度120℃下對該燒瓶內的殘存物進行3小時乾燥而獲得「乾燥試樣」。 (4) Dry the residue in the flask at a temperature of 120°C for 3 hours to obtain a "dry sample".
測定乾燥試樣(丙酮可溶部分)的質量,並藉由下式來算出丙酮不溶部分。 The mass of the dried sample (the acetone-soluble part) is measured, and the acetone-insoluble part is calculated by the following formula.
wais=(wc1-was)/wc1×100‧‧‧(2) w ais =(w c1 -w as )/w c1 ×100‧‧‧(2)
wc1:供於測定的含有橡膠的接枝聚合體的質量 w c1 : The mass of graft polymer containing rubber for measurement
was:丙酮可溶部分的質量 w as : the mass of the acetone soluble part
wais:丙酮不溶部分的質量。 Wais : the mass of the acetone-insoluble part.
於所述操作中,「游離聚合體Pfr」作為丙酮可溶部分來萃取。 In the operation, the "free polymer P fr "is extracted as the acetone-soluble part.
就成形體的衝擊強度的觀點而言,含有橡膠的接枝聚合體(C)中的橡膠狀聚合體的含有率(100Wrp/WC)較佳為50質量%~95質量%的範圍,更佳為70質量%~94質量%的範圍,進而更佳為75質量%~93質量%的範圍,特佳為80質量%~92質量%的範圍,最佳為85質量%~91質量%的範圍。 From the viewpoint of the impact strength of the molded body, the content rate (100W rp /W C ) of the rubber-like polymer in the rubber-containing graft polymer (C) is preferably in the range of 50% by mass to 95% by mass, More preferably, it is in the range of 70% to 94% by mass, still more preferably in the range of 75% to 93% by mass, particularly preferably in the range of 80% to 92% by mass, most preferably 85% to 91% by mass Range.
含有橡膠的接枝聚合體(C)通常可於乳化劑與水的存在下使橡膠狀聚合體變成乳膠狀態,並向其中添加乙烯基系單量體來進行接枝聚合而獲得。 The rubber-containing graft polymer (C) is usually obtained by changing the rubber-like polymer into a latex state in the presence of an emulsifier and water, and adding a vinyl monomer to it to perform graft polymerization.
作為接枝聚合時所使用的聚合起始劑,可列舉過氧化物或偶氮系起始劑等。 As the polymerization initiator used in the graft polymerization, peroxides or azo-based initiators can be cited.
作為接枝聚合時所使用的乳化劑,可列舉:脂肪酸、磺酸、硫酸、磷酸等酸的鹼金屬鹽等。就使工程塑膠與玻璃填充劑的密接性變得良好的觀點而言,作為乳化劑,較佳為磺酸、硫酸、磷酸等強酸的鹼金屬鹽。另外,就乳膠的穩定性優異,且即便殘存於含有橡膠的接枝聚合體中,亦難以使工程塑膠熱劣化這一理由而言,作為乳化劑,更佳為含有磺酸、硫酸、磷酸的有機酸的鹼金屬鹽。 Examples of emulsifiers used in graft polymerization include alkali metal salts of acids such as fatty acids, sulfonic acids, sulfuric acid, and phosphoric acid. From the viewpoint of improving the adhesion between the engineering plastic and the glass filler, the emulsifier is preferably an alkali metal salt of a strong acid such as sulfonic acid, sulfuric acid, and phosphoric acid. In addition, since latex has excellent stability and is difficult to thermally degrade engineering plastics even if it remains in a graft polymer containing rubber, the emulsifier is preferably one containing sulfonic acid, sulfuric acid, and phosphoric acid. Alkali metal salts of organic acids.
[鹼金屬與強酸的鹽(D)] [Alkali metal and strong acid salt (D)]
本發明的樹脂組成物中所含有的鹼金屬與強酸的鹽(D)可 作為含有橡膠的接枝聚合體(C)的聚合時所使用的乳化劑等而事先包含於含有橡膠的接枝聚合體(C)中,亦可其後添加於包含工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的樹脂組成物中。 The alkali metal and strong acid salt (D) contained in the resin composition of the present invention can be As an emulsifier used in the polymerization of the rubber-containing graft polymer (C), it is included in the rubber-containing graft polymer (C) in advance, and it can also be added to the rubber-containing graft polymer (A) and glass. The filler (B) and the resin composition of the graft polymer (C) containing rubber.
於本發明中,所謂「強酸」,是指pKa(-logKa)為2以下者。再者,「Ka」為酸解離常數。作為強酸,例如可列舉:氯化氫、硫酸、磷酸、硝酸、磺酸等。另外,於本發明中,所謂「鹼金屬」,是指元素週期表中相當於1族的元素中的氫以外的元素,鈉、鉀等符合。 In the present invention, the "strong acid" refers to a pKa (-logKa) of 2 or less. Furthermore, "Ka" is the acid dissociation constant. Examples of strong acids include hydrogen chloride, sulfuric acid, phosphoric acid, nitric acid, and sulfonic acid. In addition, in the present invention, the "alkali metal" refers to elements other than hydrogen among the elements corresponding to Group 1 in the periodic table, and sodium, potassium, etc. correspond.
作為鹼金屬與強酸的鹽(D),較佳為磺酸、硫酸、磷酸的鹼金屬鹽,例如可列舉以下者。過硫酸鉀、過硫酸鈉;全氟烷烴磺酸的鹼金屬鹽,具有較佳為碳數1~19的全氟烷烴基,更佳為碳數4~8的全氟烷烴基的磺酸等的鈉鹽或鉀鹽(例如全氟丁磺酸、全氟甲基丁磺酸、全氟辛磺酸等的鈉鹽或鉀鹽);第一磷酸的鈉鹽或鉀鹽、第二磷酸的鈉鹽或鉀鹽、第三磷酸的鈉鹽或鉀鹽;含有磺酸、硫酸、磷酸的有機酸的鹼金屬鹽,更佳為烷基磺酸或烷基芳基磺酸的鈉鹽或鉀鹽;烷基硫酸或烷基芳基硫酸的鈉鹽或鉀鹽;烷基磷酸或烷基芳基磷酸的鈉鹽或鉀鹽等。就乳膠的穩定性優異,且即便殘存於含有橡膠的接枝聚合體(C)中,對於工程塑膠(A)的熱劣化的不良影響亦少而言,作為鹼金屬與強酸的鹽(D),較佳為含有磺酸、硫酸、磷酸的有機酸的鹼金屬鹽。更佳為烷基磺酸或烷基芳基磺酸的鈉鹽或鉀鹽、烷基硫酸或烷基芳基 硫酸的鈉鹽或鉀鹽、烷基磷酸或烷基芳基磷酸的鈉鹽或鉀鹽、該些的混合物。 The salt (D) of an alkali metal and a strong acid is preferably an alkali metal salt of sulfonic acid, sulfuric acid, and phosphoric acid, and examples thereof include the following. Potassium persulfate, sodium persulfate; Alkali metal salt of perfluoroalkane sulfonic acid, preferably having a perfluoroalkane group having 1 to 19 carbon atoms, more preferably a perfluoroalkane group having 4 to 8 carbon atoms, etc. The sodium or potassium salt of (for example, the sodium or potassium salt of perfluorobutane sulfonic acid, perfluoromethyl butane sulfonic acid, perfluorooctane sulfonic acid, etc.); the sodium or potassium salt of the first phosphoric acid Sodium salt or potassium salt, sodium salt or potassium salt of tertiary phosphoric acid; alkali metal salt of organic acid containing sulfonic acid, sulfuric acid, phosphoric acid, more preferably sodium salt or potassium of alkyl sulfonic acid or alkyl aryl sulfonic acid Salt; sodium or potassium salt of alkyl sulfuric acid or alkyl aryl sulfuric acid; sodium or potassium salt of alkyl phosphoric acid or alkyl aryl phosphoric acid, etc. Since latex is excellent in stability, and even if it remains in the rubber-containing graft polymer (C), it has little adverse effect on the thermal degradation of the engineering plastic (A), as a salt of alkali metal and strong acid (D) It is preferably an alkali metal salt of an organic acid containing sulfonic acid, sulfuric acid, and phosphoric acid. More preferably, sodium or potassium salt of alkyl sulfonic acid or alkyl aryl sulfonic acid, alkyl sulfuric acid or alkyl aryl The sodium or potassium salt of sulfuric acid, the sodium or potassium salt of alkyl phosphoric acid or alkyl aryl phosphoric acid, and a mixture of these.
作為鹼金屬與強酸的鹽(D),具體而言,可列舉以下者。全氟丁磺酸鉀、二苯基碸磺酸鉀、對甲苯磺酸鉀、對甲苯磺酸鈉、十二基苯磺酸鈉、辛基苯磺酸鉀、月桂基硫酸鈉、烷基萘基磺酸鈉、烷基二苯基醚二磺酸鈉、C8-C16烷基化二苯基醚二磺酸鈉、己基磷酸鉀、十二基磷酸鈉、聚氧化乙烯烷基(12~15)醚磷酸鈉、及該些的混合物等。鈉或鉀與磺酸的鹽不會促進碳酸酯鍵或酯鍵等的水解,故較佳,更佳為十二基苯磺酸鈉或烷基二苯基醚二磺酸鈉等烷基磺酸鈉、及全氟丁磺酸鉀或二苯基碸磺酸鉀等磺酸鉀。烷基二苯基醚二磺酸鈉或二苯基碸磺酸鉀因與芳香族聚碳酸酯樹脂的相容性良好、及不會使該樹脂熱劣化,故特佳。 As the salt (D) of an alkali metal and a strong acid, the following are specifically mentioned. Potassium perfluorobutane sulfonate, potassium diphenyl sulfonate, potassium p-toluene sulfonate, sodium p-toluene sulfonate, sodium dodecylbenzene sulfonate, potassium octylbenzene sulfonate, sodium lauryl sulfate, alkyl naphthalene Sodium sulfonate, sodium alkyl diphenyl ether disulfonate, C8-C16 alkylated sodium diphenyl ether disulfonate, potassium hexyl phosphate, sodium dodecyl phosphate, polyoxyethylene alkyl (12~15 ) Sodium ether phosphate, and mixtures of these. The salt of sodium or potassium and sulfonic acid does not promote the hydrolysis of carbonate bonds or ester bonds, and is therefore preferred, more preferably alkyl sulfonates such as sodium dodecylbenzene sulfonate or sodium alkyl diphenyl ether disulfonate Sodium, and potassium perfluorobutane sulfonate or potassium diphenyl sulfonate. Sodium alkyl diphenyl ether disulfonate or potassium diphenyl sulfonate is particularly preferred because it has good compatibility with the aromatic polycarbonate resin and does not thermally degrade the resin.
[脂肪酸] [fatty acid]
於本發明中,所謂「脂肪酸」,是指含有羧酸的烴化合物。當於接枝聚合時將脂肪酸的鹼金屬鹽用作乳化劑時,若向所獲得的含有橡膠的接枝聚合體(C)的乳膠中添加作為強酸凝聚劑的硫酸、磷酸等,則作為乳化劑的脂肪酸的鹼金屬鹽變成水溶性低的脂肪酸。其結果,含有橡膠的接枝聚合體(C)與水分離,因此可回收含有橡膠的接枝聚合體(C)。因此,於該情況下,所製造的含有橡膠的接枝聚合體(C)中含有脂肪酸。脂肪酸會對玻璃填充劑(B)與工程塑膠(A)的密接性造成影響,因此較佳為含有橡膠的接枝聚合體(C)中所含的脂肪酸的量少。本發明的樹脂組成 物100質量份中的脂肪酸的含量較佳為0.03質量份以下,更佳為0.02質量份以下,進而更佳為0.01質量份以下。另外,最佳為該含量為0.01質量份以下,且於測定脂肪酸時,檢測不出棕櫚酸、硬脂酸、油酸、烯基丁二酸、松香酸。 In the present invention, the "fatty acid" refers to a hydrocarbon compound containing a carboxylic acid. When an alkali metal salt of a fatty acid is used as an emulsifier during graft polymerization, if sulfuric acid, phosphoric acid, etc., as a strong acid flocculant are added to the obtained latex of the rubber-containing graft polymer (C), it is used as an emulsification The alkali metal salt of the fatty acid of the agent becomes a fatty acid with low water solubility. As a result, the rubber-containing graft polymer (C) is separated from water, so the rubber-containing graft polymer (C) can be recovered. Therefore, in this case, the produced rubber-containing graft polymer (C) contains fatty acids. The fatty acid affects the adhesion between the glass filler (B) and the engineering plastic (A). Therefore, it is preferable that the amount of fatty acid contained in the rubber-containing graft polymer (C) is small. The resin composition of the present invention The content of the fatty acid in 100 parts by mass of the substance is preferably 0.03 parts by mass or less, more preferably 0.02 parts by mass or less, and still more preferably 0.01 parts by mass or less. In addition, it is best that the content is 0.01 parts by mass or less, and palmitic acid, stearic acid, oleic acid, alkenyl succinic acid, and rosin acid are not detected when measuring fatty acids.
另外,含有橡膠的接枝聚合體(C)中所含的脂肪酸的含量較佳為1質量%以下,更佳為0.5質量%以下,進而更佳為0.25質量%以下,特佳為0.1質量%以下。 In addition, the content of the fatty acid contained in the rubber-containing graft polymer (C) is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.25% by mass or less, particularly preferably 0.1% by mass the following.
關於脂肪酸的檢測法,例如可列舉:對羧酸進行酯化處理,並利用最合適的溶媒對所獲得的羧酸酯進行萃取,然後藉由氣相層析法來進行檢測,並進行定量的方法。 As for the detection method of fatty acids, for example, the carboxylic acid is esterified, and the obtained carboxylic acid ester is extracted with the most suitable solvent, and then detected by gas chromatography and quantitatively determined method.
作為脂肪酸的鹼金屬鹽即聚合乳化劑,於工業上大量使用棕櫚酸、硬脂酸、油酸、烯基丁二酸、松香酸的鹼金屬鹽。因此,於製法不明的含有橡膠的接枝聚合體(C)的商品中,可限定為棕櫚酸、硬脂酸、油酸、烯基丁二酸、松香酸來對脂肪酸的量進行定量。含有橡膠的接枝聚合體(C)中所含的棕櫚酸、硬脂酸、油酸、烯基丁二酸、松香酸的量較佳為如上所述(1質量%以下)。 As the alkali metal salt of fatty acid, that is, the polymeric emulsifier, the alkali metal salt of palmitic acid, stearic acid, oleic acid, alkenyl succinic acid, and rosin acid is widely used in industry. Therefore, in the commercial product of the rubber-containing graft polymer (C) whose production method is unknown, palmitic acid, stearic acid, oleic acid, alkenyl succinic acid, and rosin acid can be limited to quantify the amount of fatty acid. The amount of palmitic acid, stearic acid, oleic acid, alkenyl succinic acid, and rosin acid contained in the rubber-containing graft polymer (C) is preferably as described above (1% by mass or less).
為了使本發明的樹脂組成物100質量份中的脂肪酸的含量變成0.03質量份以下,較佳為於對含有橡膠的接枝聚合體(C)進行聚合時,在加入的階段,將含有橡膠的接枝聚合體(C)與「包含脂肪酸的乳化劑」(脂肪酸的鹼金屬鹽)的合計100質量%中的「包含脂肪酸的乳化劑」設為例如0.03質量%以下。或者,較佳為使用其他乳化劑來代替「包含脂肪酸的乳化劑」。具體而言,就 減少含有橡膠的接枝聚合體(C)中的脂肪酸的量的觀點而言,較佳為在作為鹼金屬與強酸的鹽(D)的聚合乳化劑及去離子水的存在下,對以上所揭示的橡膠狀聚合體進行聚合,繼而使乙烯基系單量體進行接枝聚合。 In order to reduce the content of fatty acids in 100 parts by mass of the resin composition of the present invention to 0.03 parts by mass or less, it is preferable that the rubber-containing graft polymer (C) is polymerized at the stage of addition. The "emulsifier containing fatty acid" in the total 100% by mass of the graft polymer (C) and the "emulsifier containing fatty acid" (alkali metal salt of fatty acid) is set to, for example, 0.03% by mass or less. Alternatively, it is preferable to use other emulsifiers instead of "fatty acid-containing emulsifiers". Specifically, in terms of From the standpoint of reducing the amount of fatty acids in the rubber-containing graft polymer (C), it is preferable to treat the above mentioned in the presence of a polymeric emulsifier as a salt of an alkali metal and a strong acid (D) and deionized water. The disclosed rubber-like polymer is polymerized, and then the vinyl monomer is graft-polymerized.
[含有橡膠的接枝聚合體(C)的回收] [Recovery of graft polymer (C) containing rubber]
藉由接枝聚合所獲得的乳膠狀態的含有橡膠的接枝聚合體(C)可藉由進行凝聚並清洗後加以乾燥、或藉由進行噴霧回收而作為粉體獲得。 The rubber-containing graft polymer (C) in the latex state obtained by graft polymerization can be obtained as a powder by coagulating, washing, and then drying, or by spraying and recovering.
含有橡膠的接枝聚合體(C)較佳為使用凝聚劑對含有橡膠的接枝聚合體乳膠進行凝聚回收所獲得者、或進行噴霧回收所獲得者,所述含有橡膠的接枝聚合體乳膠是在包含鹼金屬與強酸的鹽(D)的橡膠乳膠的存在下,使乙烯基單量體進行乳化聚合而獲得,更佳為進行噴霧回收所獲得者。 The rubber-containing graft polymer (C) is preferably obtained by coagulating and recovering a rubber-containing graft polymer latex using a coagulant, or obtained by spraying and recovering, the rubber-containing graft polymer latex It is obtained by emulsion polymerization of a vinyl monomer in the presence of a rubber latex containing the salt (D) of an alkali metal and a strong acid, and it is more preferably obtained by spray recovery.
當將鹼金屬與強酸的鹽(D)作為乳化劑進行接枝聚合,並對含有橡膠的接枝聚合體(C)進行噴霧回收時,乳化劑以鹼金屬與強酸的鹽(D)的狀態殘存於含有橡膠的接枝聚合體(C)中,故較佳。 When the alkali metal and strong acid salt (D) is used as an emulsifier for graft polymerization and the rubber-containing graft polymer (C) is sprayed and recovered, the emulsifier is in the state of alkali metal and strong acid salt (D) It is preferable because it remains in the graft polymer (C) containing rubber.
當將鹼金屬與強酸的鹽(D)作為乳化劑進行接枝聚合,並利用凝聚法對含有橡膠的接枝聚合體(C)進行回收時,較佳為使用包含鹼土金屬(2族)或鋁等土類金屬(13族)的鹽(氯化鈣、乙酸鈣、硫酸鋁等)作為凝聚劑,於清洗時使用大量的水,並有效地利用離心分離機等來充分地去除漿料中的水分。使用所 述凝聚劑的理由在於:於使用酸作為凝聚劑時,必須使用pKa低於「鹼金屬與強酸的鹽(D)」的「強酸」的酸,但若此種強酸殘存於含有橡膠的接枝聚合體(C)中,則會使工程塑膠(A)劣化。於使用所述凝聚劑的凝聚的過程中,用作乳化劑的「鹼金屬與強酸的鹽(D)」變成「鹼土金屬與強酸的鹽」或「土類金屬(13族)與強酸的鹽」。鹼土金屬與強酸的鹽、及土類金屬(13族)與強酸的鹽因水溶性低,故可使乳膠中的聚合物粒子凝聚。其結果,因含有橡膠的接枝聚合體(C)與水分離,故可回收含有橡膠的接枝聚合體(C)。若對凝聚物進行清洗並加以乾燥,則可獲得含有橡膠的接枝聚合體(C)的粉體。但是,與鹼金屬與強酸的鹽(D)相比,鹼土金屬與強酸的鹽、或鋁等土類金屬(13族)與強酸的鹽會使工程塑膠(A)與玻璃填充劑(B)的密接性下降。源自含有橡膠的接枝聚合體(C)的鈣與強酸的鹽、鎂與強酸的鹽及鋁與強酸的鹽會顯著地使所述密接性下降。因此,較佳為利用水等對經凝聚的聚合物粒子(漿料)進行清洗。 When the alkali metal and strong acid salt (D) is used as an emulsifier for graft polymerization, and the rubber-containing graft polymer (C) is recovered by a coacervation method, it is preferable to use an alkaline earth metal (group 2) or Aluminium and other earth metal (group 13) salts (calcium chloride, calcium acetate, aluminum sulfate, etc.) are used as agglomerating agents, and a large amount of water is used for cleaning, and a centrifugal separator is effectively used to fully remove the slurry Of moisture. Used by The reason for the flocculant is that when an acid is used as a flocculant, it is necessary to use a "strong acid" with a pKa lower than the "alkali metal and strong acid salt (D)", but if such a strong acid remains in the graft containing rubber In the polymer (C), the engineering plastic (A) is deteriorated. In the process of coagulation using the flocculant, the "alkali metal and strong acid salt (D)" used as an emulsifier becomes "alkaline earth metal and strong acid salt" or "earth metal (group 13) and strong acid salt" ". Salts of alkaline earth metals and strong acids and salts of earth metals (group 13) and strong acids have low water solubility, so they can aggregate polymer particles in the latex. As a result, since the rubber-containing graft polymer (C) is separated from water, the rubber-containing graft polymer (C) can be recovered. If the agglomerate is washed and dried, a powder of the graft polymer (C) containing rubber can be obtained. However, compared with the salt of alkali metal and strong acid (D), the salt of alkaline earth metal and strong acid, or the salt of earth metal (group 13) such as aluminum and the salt of strong acid will make engineering plastics (A) and glass fillers (B) The closeness of the adhesive decreases. A salt of calcium and a strong acid, a salt of magnesium and a strong acid, and a salt of aluminum and a strong acid derived from the rubber-containing graft polymer (C) significantly reduce the adhesion. Therefore, it is preferable to wash the aggregated polymer particles (slurry) with water or the like.
[樹脂組成物] [Resin composition]
本發明的樹脂組成物是包含工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的組成物。於以下的說明中,有時將工程塑膠(A)及含有橡膠的接枝聚合體(C)稱為樹脂組成物的「樹脂二成分」。另外,有時將工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)稱為樹脂組成物的「主要三成分」。 The resin composition of the present invention is a composition containing engineering plastic (A), glass filler (B), and graft polymer (C) containing rubber. In the following description, the engineering plastic (A) and the rubber-containing graft polymer (C) may be referred to as the "resin two components" of the resin composition. In addition, engineering plastic (A), glass filler (B), and rubber-containing graft polymer (C) are sometimes referred to as the "main three components" of the resin composition.
[源自丙烯腈的成分的比例] [Proportion of ingredients derived from acrylonitrile]
本發明的樹脂組成物的氯仿可溶部分中的源自丙烯腈的成分的比例較佳為2.0質量%以下。所謂「源自丙烯腈的成分」,是指「游離聚合體Pfr」中所含的丙烯腈構成成分。雖然已進行了說明,但於作為粉體集合物所回收的含有橡膠的接枝聚合體(C)中,作為「非接枝成分」的「游離聚合體Pfr」混合存在。因此,於樹脂組成物的氯仿可溶部分中,包含工程塑膠(A)與作為「非接枝成分」的「游離聚合體Pfr」。 The ratio of the acrylonitrile-derived component in the chloroform-soluble part of the resin composition of the present invention is preferably 2.0% by mass or less. The "component derived from acrylonitrile" refers to the acrylonitrile component contained in the "free polymer P fr ". Although it has been described, in the rubber-containing graft polymer (C) recovered as a powder aggregate, the "free polymer P fr "as the "non-grafted component" is mixed. Therefore, the chloroform-soluble part of the resin composition contains engineering plastic (A) and "free polymer P fr "as a "non-grafted component".
樹脂組成物的氯仿可溶部分中的源自丙烯腈的成分可藉由如下方式來定量:製備包含樹脂組成物1質量%、氯仿99質量%的溶液,並進行以下的(1)~(4)的操作,且算出所獲得的「乾燥試樣」中的丙烯腈的量。 The acrylonitrile-derived component in the chloroform-soluble part of the resin composition can be quantified by preparing a solution containing 1% by mass of the resin composition and 99% by mass of chloroform, and performing the following (1) to (4) ) And calculate the amount of acrylonitrile in the "dry sample" obtained.
(1)將所述溶液供於離心分離機並以20000rpm進行30分鐘離心分離。 (1) The solution was supplied to a centrifuge and centrifuged at 20000 rpm for 30 minutes.
(2)對上清液進行萃取,並放入至燒瓶內。 (2) Extract the supernatant and put it into the flask.
(3)將該燒瓶設置於溫度為68℃的恆溫槽中,並利用蒸發器自該上清液中餾去揮發成分。 (3) The flask was set in a constant temperature bath at a temperature of 68°C, and volatile components were distilled off from the supernatant with an evaporator.
(4)於溫度120℃下對該燒瓶內的殘存物進行3小時乾燥而獲得「乾燥試樣」。 (4) Dry the residue in the flask at a temperature of 120°C for 3 hours to obtain a "dry sample".
作為「乾燥試樣」中的丙烯腈的量的算出方法,較佳為利用氣相層析法進行檢測,並進行定量的方法。當於「乾燥試樣」中不存在丙烯腈以外的含有氮的化合物時,亦可進行元素分析,並根據其氮含有率來算出。 As a method of calculating the amount of acrylonitrile in the "dry sample", a method of detecting and quantifying by gas chromatography is preferred. When there are no nitrogen-containing compounds other than acrylonitrile in the "dry sample", elemental analysis can also be performed, and the calculation can be based on the nitrogen content.
再者,選定氯仿而非丙酮作為溶媒的原因在於:對於工程塑膠(A)的溶解性,氯仿比丙酮高。尤其當工程塑膠(A)為芳香族聚碳酸酯樹脂時,氯仿最合適。就提昇成形體的衝擊強度的觀點而言,樹脂組成物的氯仿可溶部分中的源自丙烯腈的成分更佳為1.5質量%以下,進而更佳為0.8質量%以下,特佳為0.5質量%以下。 Furthermore, the reason for choosing chloroform instead of acetone as the solvent is that the solubility of engineering plastic (A) is higher than that of acetone. Especially when the engineering plastic (A) is an aromatic polycarbonate resin, chloroform is most suitable. From the viewpoint of improving the impact strength of the molded body, the acrylonitrile-derived component in the chloroform-soluble part of the resin composition is more preferably 1.5% by mass or less, still more preferably 0.8% by mass or less, and particularly preferably 0.5% by mass %the following.
對於橡膠狀聚合體進行接枝聚合的乙烯基系單量體較佳為甲基丙烯酸甲酯與丙烯酸丁酯的共聚物、苯乙烯與丙烯腈的共聚物(丙烯腈單元的比率為35質量%以下)。同時,含有橡膠的接枝聚合體(C)中的橡膠狀聚合體的含有率較佳為50質量%~95質量%的範圍,進而,較佳為與橡膠狀聚合體進行化學鍵結的接枝成分的量多,因此丙酮不溶部分更佳為83質量%以上。當接枝聚合體中的丙烯腈單元的比率為35質量%以下且丙酮可溶部分為83質量%以上時,於相對於「主要三成分」的合計100質量%的玻璃填充劑(B)的含量為5質量%~40質量%、且含有橡膠的接枝聚合體(C)的含量為0.25質量%~15質量%的樹脂組成物中,氯仿可溶部分的源自丙烯腈的成分可設為2.0質量%以下。 The vinyl monomer for graft polymerization of the rubbery polymer is preferably a copolymer of methyl methacrylate and butyl acrylate, a copolymer of styrene and acrylonitrile (the ratio of acrylonitrile units is 35% by mass the following). At the same time, the content of the rubber-like polymer in the rubber-containing graft polymer (C) is preferably in the range of 50% by mass to 95% by mass, and more preferably a graft that chemically bonds with the rubber-like polymer Since the amount of components is large, the acetone-insoluble portion is more preferably 83% by mass or more. When the ratio of the acrylonitrile unit in the graft polymer is 35% by mass or less and the acetone-soluble part is 83% by mass or more, the ratio of the glass filler (B) relative to the total of 100% by mass of the "main three components" In a resin composition with a content of 5% to 40% by mass and a rubber-containing graft polymer (C) content of 0.25% to 15% by mass, the chloroform-soluble part of the acrylonitrile-derived component can be set It is 2.0% by mass or less.
於本發明的樹脂組成物中,於「主要三成分」合計100質量%中,工程塑膠(A)的含量較佳為95質量%~60質量%。其含量更佳為80質量%~60質量%,進而更佳為80質量%~70質量%。若其含量為60質量%以上,則樹脂組成物的成形加工性容易,若為95質量%以下,則樹脂組成物的成形體具有充分的彎曲 特性(強度、彈性係數)。 In the resin composition of the present invention, the content of the engineering plastic (A) is preferably 95% by mass to 60% by mass in a total of 100% by mass of the "main three components". The content thereof is more preferably 80% by mass to 60% by mass, and still more preferably 80% by mass to 70% by mass. If its content is 60% by mass or more, the molding processability of the resin composition is easy, and if it is 95% by mass or less, the molded body of the resin composition has sufficient curvature. Characteristics (strength, elastic coefficient).
於本發明的樹脂組成物中,於「主要三成分」的合計100質量%中,玻璃填充劑(B)的含量較佳為5質量%~40質量%。其含量更佳為10質量%~40質量%,進而更佳為20質量%~30質量%。若其含量為5質量%以上,則樹脂組成物的成形體可具有充分的彎曲特性(強度、彈性係數),若為40質量%以下,則樹脂組成物的成形體成為查皮衝擊強度與彎曲特性的平衡充分者。 In the resin composition of the present invention, the content of the glass filler (B) is preferably 5 to 40% by mass in the total 100% by mass of the "main three components". The content thereof is more preferably 10% by mass to 40% by mass, and still more preferably 20% by mass to 30% by mass. If its content is 5% by mass or more, the molded body of the resin composition can have sufficient bending properties (strength, elastic modulus), and if it is 40% by mass or less, the molded body of the resin composition will have the skin impact strength and bending Those with sufficient balance of characteristics.
於本發明的樹脂組成物中,於「主要三成分」的合計100質量%中,含有橡膠的接枝聚合體(C)的含量較佳為0.25質量%~15質量%。其含量更佳為0.25質量%~7.5質量%,進而更佳為1質量%~3質量%。若其含量為0.25質量%以上,則樹脂組成物的成形體具有衝擊強度的改良效果。若其含量為15質量%以下,則成形體無彎曲特性(強度、彈性係數)的顯著下降的情況,並可改良衝擊強度。 In the resin composition of the present invention, the content of the graft polymer (C) containing rubber in the total 100% by mass of the "main three components" is preferably 0.25% by mass to 15% by mass. The content thereof is more preferably 0.25% by mass to 7.5% by mass, and still more preferably 1% by mass to 3% by mass. If the content is 0.25% by mass or more, the molded body of the resin composition has the effect of improving impact strength. If the content is 15% by mass or less, the formed body does not significantly decrease in bending properties (strength, elastic modulus), and the impact strength can be improved.
於本發明的第一形態的樹脂組成物中,就工程塑膠(A)與玻璃填充劑(B)的密接性良好這一點而言,樹脂組成物100質量份中的脂肪酸的含量較佳為0.03質量份以下。另外,更佳為檢測不出棕櫚酸、硬脂酸、油酸、烯基丁二酸、松香酸(0.01質量份以下)。 In the resin composition of the first aspect of the present invention, the content of fatty acid in 100 parts by mass of the resin composition is preferably 0.03 in terms of good adhesion between the engineering plastic (A) and the glass filler (B) Parts by mass or less. In addition, it is more preferable that palmitic acid, stearic acid, oleic acid, alkenyl succinic acid, and rosin acid (0.01 parts by mass or less) are not detected.
本發明的樹脂組成物較佳為進而含有鹼金屬與強酸的鹽(D),其原因在於:工程塑膠(A)與玻璃填充劑(B)的密接性優異。本發明的樹脂組成物100質量份中的鹼金屬與強酸的鹽 (D)的含量較佳為0.01質量份~0.5質量份。該含量更佳為0.2質量份以下,進而更佳為0.02質量份~0.15質量份。若該含量為0.01質量份以上,則工程塑膠(A)與玻璃填充劑(B)的密接性優異,故較佳。若該含量為0.5質量份以下,則樹脂組成物的成形時的熱劣化或成形體的水解性不會成為問題,故較佳。 The resin composition of the present invention preferably further contains a salt (D) of an alkali metal and a strong acid because the engineering plastic (A) and the glass filler (B) have excellent adhesiveness. Salt of alkali metal and strong acid in 100 parts by mass of the resin composition of the present invention The content of (D) is preferably 0.01 parts by mass to 0.5 parts by mass. The content is more preferably 0.2 parts by mass or less, and still more preferably 0.02 parts by mass to 0.15 parts by mass. If the content is 0.01 parts by mass or more, the adhesiveness between the engineering plastic (A) and the glass filler (B) is excellent, which is preferable. If the content is 0.5 parts by mass or less, thermal deterioration during molding of the resin composition or hydrolyzability of the molded body will not be a problem, so it is preferred.
鹼金屬與強酸的鹽(D)可作為含有橡膠的接枝聚合體(C)的接枝聚合時所使用的乳化劑等而事先包含於含有橡膠的接枝聚合體(C)中,亦可其後添加於包含工程塑膠(A)、玻璃填充劑(B)及含有橡膠的接枝聚合體(C)的樹脂組成物中。 The salt of alkali metal and strong acid (D) may be included in the rubber-containing graft polymer (C) in advance as an emulsifier used in the graft polymerization of the rubber-containing graft polymer (C), or It is then added to a resin composition containing engineering plastic (A), glass filler (B), and rubber-containing graft polymer (C).
[鈣、鎂] [Calcium, Magnesium]
樹脂組成物中的鈣或鎂與強酸的鹽會降低工程塑膠(A)與玻璃填充劑(B)的密接性,促進樹脂組成物的成形時的熱劣化,並顯著地使成形體的高溫高濕下的耐水解性等性質惡化。尤其源自含有橡膠的接枝聚合體(C)的鈣或鎂與強酸的鹽會顯著地使工程塑膠(A)與玻璃填充劑(B)的密接性惡化。 The salt of calcium or magnesium and strong acid in the resin composition reduces the adhesion between the engineering plastic (A) and the glass filler (B), promotes thermal degradation during the molding of the resin composition, and significantly increases the high temperature of the molded body Properties such as hydrolysis resistance under wet conditions deteriorate. In particular, the salt of calcium or magnesium derived from a rubber-containing graft polymer (C) and a strong acid significantly deteriorates the adhesion between the engineering plastic (A) and the glass filler (B).
於本發明的第一形態的樹脂組成物中,藉由以下的測定方法X所測定的乾燥試樣100質量份中的鈣及鎂的合計含量為0.0008質量份以下(8ppm以下)。若鈣及鎂換算的合計含量的值為該範圍內,則所述工程塑膠(A)與玻璃填充劑(B)的密接性、樹脂組成物的成形時的熱劣化或成形體的水解性不會成為問題,因此成形體的衝擊強度或彎曲特性(彈性係數及強度)優異。該鈣及鎂換算的合計含量更佳為0.0006質量份以下(6ppm以下), 進而更佳為0.0002質量份以下(2ppm以下)。 In the resin composition of the first aspect of the present invention, the total content of calcium and magnesium in 100 parts by mass of a dry sample measured by the following measuring method X is 0.0008 parts by mass or less (8 ppm or less). If the total content in terms of calcium and magnesium is within this range, the adhesiveness of the engineering plastic (A) and the glass filler (B), the thermal degradation of the resin composition during molding, or the hydrolysis of the molded body are not It becomes a problem, and therefore the impact strength and bending characteristics (elasticity and strength) of the molded body are excellent. The total content in terms of calcium and magnesium is more preferably 0.0006 parts by mass or less (6 ppm or less), More preferably, it is 0.0002 parts by mass or less (2 ppm or less).
[測定方法X] [Measurement method X]
製備包含樹脂組成物5質量%及氯仿95質量%的溶液,並進行以下(1)~(4)的操作而獲得「乾燥試樣」。繼而,測定乾燥試樣100質量份中的鈣、鎂及鋁的質量。 A solution containing 5% by mass of the resin composition and 95% by mass of chloroform was prepared, and the following operations (1) to (4) were performed to obtain a "dry sample". Then, the masses of calcium, magnesium, and aluminum in 100 parts by mass of the dried sample were measured.
(1)將所述溶液供於離心分離機並以5000rpm進行30分鐘離心分離。 (1) The solution is supplied to a centrifuge and centrifuged at 5000 rpm for 30 minutes.
(2)對上清液進行萃取,並放入至燒瓶內。 (2) Extract the supernatant and put it into the flask.
(3)將該燒瓶設置於溫度為68℃的恆溫槽中,並利用蒸發器自該上清液中餾去揮發成分。 (3) The flask was set in a constant temperature bath at a temperature of 68°C, and volatile components were distilled off from the supernatant with an evaporator.
(4)於溫度120℃下對該燒瓶內的殘存物進行3小時乾燥而獲得「乾燥試樣」。 (4) Dry the residue in the flask at a temperature of 120°C for 3 hours to obtain a "dry sample".
可溶於先前所述的氯仿中的樹脂組成物與藉由測定方法X的(4)所獲得的「乾燥試樣」相同。藉由測定「乾燥試樣」中的鈣量及鎂量,可大致將本發明的樹脂組成物中的鈣或鎂與強酸的鹽的合計含量「Wcas+mgs」作為鈣及鎂換算的合計含量「Wca+mg」來求出。其理由在於:鈣或鎂與弱酸的鹽、特別是鈣或鎂與脂肪酸的鹽難以溶解於氯仿中,及玻璃填充劑(B)難以溶解於氯仿中。藉由測定樹脂組成物中的氯仿可溶部分的鈣量、鎂量,大致可測定來自源自含有橡膠的接枝聚合體(C)的鈣或鎂與強酸的鹽的鈣量、鎂量。另外,玻璃填充劑(B)有時包含鈣、鎂(鈣或鎂與矽酸的鹽),但玻璃填充劑(B)難以溶解於氯仿中,因此於樹脂組 成物中的氯仿可溶部分中,實質上不含源自玻璃填充劑(B)的鈣、鎂。 The resin composition soluble in the aforementioned chloroform is the same as the "dry sample" obtained by (4) of the measurement method X. By measuring the amount of calcium and magnesium in the "dry sample", the total content "W cas+mgs " of the salt of calcium or magnesium and strong acid in the resin composition of the present invention can be roughly regarded as the total converted into calcium and magnesium The content is calculated by "W ca+mg ". The reason is that the salt of calcium or magnesium and a weak acid, especially the salt of calcium or magnesium and a fatty acid, is difficult to dissolve in chloroform, and the glass filler (B) is difficult to dissolve in chloroform. By measuring the amount of calcium and magnesium in the chloroform-soluble part of the resin composition, it is possible to roughly measure the amount of calcium and magnesium derived from calcium or a salt of magnesium and a strong acid derived from the rubber-containing graft polymer (C). In addition, the glass filler (B) sometimes contains calcium and magnesium (a salt of calcium or magnesium and silicic acid), but the glass filler (B) is difficult to dissolve in chloroform, so it is included in the chloroform-soluble part of the resin composition , Substantially free of calcium and magnesium derived from glass filler (B).
再者,於工程塑膠(A)與玻璃填充劑(B)中,基本上不含鈣或鎂與強酸的鹽。有時於玻璃填充劑(B)中包含鈣、鎂,採用非晶結構的二氧化矽於骨架中包含鎂或鈣作為離子。矽酸並非強酸,因此於玻璃填充劑(B)中,基本上不含鈣或鎂與強酸的鹽。 Furthermore, in engineering plastics (A) and glass fillers (B), there is basically no calcium or magnesium and strong acid salts. Sometimes the glass filler (B) contains calcium and magnesium, and the amorphous structure of silicon dioxide is used to contain magnesium or calcium as ions in the framework. Silicic acid is not a strong acid, so in the glass filler (B), there is basically no calcium or magnesium salt with a strong acid.
所述「Wcas+mgs」及「Wca+mg」藉由下式來算出。 The "W cas+mgs " and "W ca+mg " are calculated by the following formula.
Wca+mg=Wca+Wmg‧‧‧‧‧(3) W ca+mg =W ca +W mg ‧‧‧‧‧(3)
Wcas+mgs=Wcas+Wmgs‧‧‧(4) W cas+mgs =W cas +W mgs ‧‧‧(4)
Wcas:鈣與強酸的鹽的含量 W cas :The content of calcium and strong acid salt
Wmgs:鎂與強酸的鹽的含量 W mgs : the content of magnesium and strong acid salt
Wca:鈣的含量 W ca : the content of calcium
Wmg:鎂的含量。 W mg : the content of magnesium.
較佳為確認以下情況:將僅包含不含鈣、鎂及鋁的工程塑膠(A)與包含鈣、鎂及鋁的玻璃填充劑(B)這兩種成分的樹脂組成物作為測定試樣來實施測定方法X,並以將源自玻璃填充劑(B)的鈣及鎂萃取至樹脂組成物中的氯仿可溶部分中而檢測不出的方式進行所述(2)的「上清液的萃取」。進行測定的結果為,當於「乾燥試樣」100質量份中,鈣及鎂的合計含量為0.0006質 量份以上(6ppm以上)及/或鋁的含量為0.0006質量份以上(6ppm以上)時,表示其上清液的萃取方法不適當。於此情況下,當對上清液進行萃取時,較佳為使用具有比玻璃填充劑(B)的直徑小、且比含有橡膠的接枝聚合體(C)的聚合體粒子的一次粒徑大的孔的過濾器(具有1μm~5μm的孔徑的耐氯仿溶解性的過濾器),對上清液進行過濾。 It is preferable to confirm the following: a resin composition containing only two components: engineering plastic (A) not containing calcium, magnesium, and aluminum, and glass filler (B) containing calcium, magnesium, and aluminum, as the measurement sample The measurement method X was carried out, and the calcium and magnesium derived from the glass filler (B) were extracted into the chloroform-soluble part of the resin composition, and the "supernatant liquid" of (2) was not detected. extraction". As a result of the measurement, in 100 parts by mass of the "dry sample", the total content of calcium and magnesium is 0.0006 mass. When the amount is greater than or equal to 6 ppm and/or the content of aluminum is greater than or equal to 0.0006 parts by mass (6 ppm or greater), it means that the extraction method of the supernatant is inappropriate. In this case, when extracting the supernatant, it is preferable to use a polymer particle having a diameter smaller than that of the glass filler (B) and larger than that of the rubber-containing graft polymer (C). A filter with large pores (a chloroform solubility-resistant filter having a pore diameter of 1 μm to 5 μm) filters the supernatant.
於「乾燥試樣」100質量份中,若鈣及鎂的合計含量為0.0008質量份以下(8ppm以下),則成形體的衝擊強度或彎曲特性(彈性係數、強度)優異。該鈣及鎂的合計含量更佳為0.0006質量份以下(6ppm以下),進而更佳為0.0002質量份以下(2ppm以下)。若「乾燥試樣」100質量份中的鈣及鎂的合計含量為0.0008質量份以下(8ppm以下),則本發明的樹脂組成物100質量份中的鈣或鎂與強酸的鹽的合計含量以鈣及鎂換算的合計含量計低於0.0008質量份(少於8ppm)。 In 100 parts by mass of the "dry sample", if the total content of calcium and magnesium is 0.0008 parts by mass or less (8 ppm or less), the impact strength or bending properties (elasticity, strength) of the molded body are excellent. The total content of calcium and magnesium is more preferably 0.0006 parts by mass or less (6 ppm or less), and still more preferably 0.0002 parts by mass or less (2 ppm or less). If the total content of calcium and magnesium in 100 parts by mass of the "dry sample" is 0.0008 parts by mass or less (8 ppm or less), the total content of calcium or magnesium and the salt of a strong acid in 100 parts by mass of the resin composition of the present invention is The total content in terms of calcium and magnesium is less than 0.0008 parts by mass (less than 8 ppm).
為了減少藉由測定方法X所測定的乾燥試樣100質量份中的鈣及鎂的合計含量、或源自含有橡膠的接枝聚合體(C)的鈣或鎂與強酸的鹽的合計含量,較佳為對含有橡膠的接枝聚合體(C)進行噴霧回收。當對含有橡膠的接枝聚合體(C)進行凝聚並加以回收時,較佳為使用包含鹼土金屬(2族)或鋁等土類金屬(13族)的鹽(氯化鈣、乙酸鈣、硫酸鎂、氯化鎂、硫酸鋁等)作為凝聚劑,於清洗時使用大量的水,並有效地利用離心分離機等來充分地去除漿料中的水分。 In order to reduce the total content of calcium and magnesium in 100 parts by mass of the dry sample measured by the measurement method X, or the total content of the salt of calcium or magnesium derived from the rubber-containing graft polymer (C) and strong acid, Preferably, the rubber-containing graft polymer (C) is sprayed and recovered. When the rubber-containing graft polymer (C) is coagulated and recovered, it is preferable to use salts (calcium chloride, calcium acetate, etc.) containing alkaline earth metals (group 2) or earth metals (group 13) such as alumina. Magnesium sulfate, magnesium chloride, aluminum sulfate, etc.) are used as agglomerating agents, and a large amount of water is used for cleaning, and centrifugal separators are effectively used to sufficiently remove the moisture in the slurry.
[鈣或鎂與強酸的鹽] [Calcium or magnesium salt with strong acid]
另外,於本發明的第二形態的樹脂組成物中,相對於本發明的樹脂組成物的「主要三成分」的合計100質量份,該樹脂組成物中的鈣或鎂與「強酸」的鹽的合計含量的鈣及鎂換算的合計含量「Tca+mg」為0.0008質量份以下。該Tca+mg的值是藉由分別算出源自含有橡膠的接枝聚合體(C)的鈣或鎂與強酸的鹽的合計含量的鈣及鎂換算的合計含量「Cca+mg」、與源自含有橡膠的接枝聚合體(C)以外的成分的鈣及鎂與強酸的鹽的合計含量的鈣及鎂換算的合計含量「NCca+mg」,並利用下式來算出。 In addition, in the resin composition of the second aspect of the present invention, with respect to the total of 100 parts by mass of the "main three components" of the resin composition of the present invention, the salt of calcium or magnesium and a "strong acid" in the resin composition The total content "T ca+mg " in terms of calcium and magnesium is 0.0008 parts by mass or less. The value of T ca+mg is calculated by calculating the total content of calcium or magnesium derived from the graft polymer (C) containing rubber (C) and the total content of the salt of a strong acid. The total content "C ca+mg ", The total content "NC ca+mg " in terms of calcium and magnesium based on the total content of calcium and magnesium derived from components other than the rubber-containing graft polymer (C) and the salt of a strong acid is calculated by the following formula.
Tca+mg=Cca+mg+NCca+mg‧‧‧(5) T ca+mg =C ca+mg +NC ca+mg ‧‧‧(5)
所述Cca+mg藉由下式來算出。 The C ca+mg is calculated by the following formula.
Cca+mg=Mc×(cqcas×rca+cqmgs×rmg)‧‧‧(6) C ca+mg =Mc×(cq cas ×r ca +cq mgs ×r mg )‧‧‧(6)
Mc:樹脂組成物的「主要三成分」100質量份中的含有橡膠的接枝聚合體(C)的質量份 Mc: parts by mass of the graft polymer (C) containing rubber in 100 parts by mass of the "main three components" of the resin composition
cqcas:含有橡膠的接枝聚合體(C)中的鈣與強酸的鹽的濃度 cq cas : The concentration of calcium and strong acid salt in the rubber-containing graft polymer (C)
cqmgs:含有橡膠的接枝聚合體(C)中的鎂與強酸的鹽的濃度 cq mgs : the concentration of the salt of magnesium and strong acid in the graft polymer (C) containing rubber
rca:鈣與強酸的鹽中的鈣濃度 r ca : Calcium concentration in the salt of calcium and strong acid
rmg:鎂與強酸的鹽中的鎂濃度。 r mg : the concentration of magnesium in the salt of magnesium and strong acid.
所述NCca+mg藉由下式來算出。 The NC ca+mg is calculated by the following formula.
NCca+mg=(mnccas×rca)+(mncmgs×rmg)‧‧‧(7) NC ca+mg =(mnc cas ×r ca )+(mnc mgs ×r mg )‧‧‧(7)
mnccas:相對於樹脂組成物的「主要三成分」的合計100質量份的樹脂組成物中的源自含有橡膠的接枝聚合體(C)以外的成分的鈣與強酸的鹽的質量份 mnc cas : The mass parts of the salt of calcium and strong acid derived from components other than the graft polymer (C) containing rubber in the total 100 parts by mass of the "main three components" of the resin composition
mncmgs:相對於樹脂組成物的「主要三成分」的合計100質量份的樹脂組成物中的源自含有橡膠的接枝聚合體(C)以外的成分的鎂與強酸的鹽的質量份 mnc mgs : The mass parts of the salt of magnesium and strong acid derived from components other than the rubber-containing graft polymer (C) in the resin composition relative to the total 100 parts by mass of the "main three components" of the resin composition
rca:鈣與強酸的鹽中的鈣濃度 r ca : Calcium concentration in the salt of calcium and strong acid
rmg:鎂與強酸的鹽中的鎂濃度。 r mg : the concentration of magnesium in the salt of magnesium and strong acid.
若所述換算含量Tca+mg為0.0008質量份以下(8ppm以下),則工程塑膠(A)與玻璃填充劑(B)的密接性、樹脂組成物的成形時的熱劣化或成形體的水解性不會成為問題,因此成形體的衝擊強度或彎曲特性(彈性係數及強度)優異。該Tca+mg的值更佳為0.0006質量份以下,進而更佳為0.0002質量份以下。 If the converted content T ca+mg is 0.0008 parts by mass or less (8 ppm or less), the adhesion between the engineering plastic (A) and the glass filler (B), the thermal deterioration of the resin composition during molding, or the hydrolysis of the molded body Since performance does not become a problem, the impact strength and bending properties (elasticity and strength) of the molded body are excellent. The value of T ca+mg is more preferably 0.0006 parts by mass or less, and still more preferably 0.0002 parts by mass or less.
[鈣或鎂與弱酸的鹽] [Calcium or magnesium with weak acid salt]
進而,於本發明的第一形態及第二形態的樹脂組成物中,樹脂組成物的「主要三成分」的合計100質量份中的玻璃填充劑(B)以外的鈣或鎂與「弱酸」的鹽的合計含量以鈣及鎂換算的合計含量「NB'ca+mg」計較佳為0.0010質量份~0.0060質量份。若該含 量NB'ca+mg的值為0.0010質量份~0.0060質量份,則成形體的衝擊強度或彎曲特性(彈性係數.強度)優異。該含量NB'ca+mg的值進而更佳為0.0020質量份~0.0030質量份。 Furthermore, in the resin composition of the first and second aspects of the present invention, calcium or magnesium other than the glass filler (B) and a "weak acid" in 100 parts by mass of the "main three components" of the resin composition The total content of the salt of Calcium and magnesium is preferably 0.0010 parts by mass to 0.0060 parts by mass in terms of the total content "NB'ca+mg" in terms of calcium and magnesium. If the value of the content NB'ca+mg is 0.0010 parts by mass to 0.0060 parts by mass, the impact strength or bending characteristics (elasticity coefficient and strength) of the molded body will be excellent. The value of this content NB'ca+mg is more preferably 0.0020 parts by mass to 0.0030 parts by mass.
於本發明中,所謂「弱酸」,是指pKa(-logKa)為3以上者。例如可列舉脂肪酸。作為鈣或鎂與弱酸的鹽,可列舉棕櫚酸鈣、棕櫚酸鎂、硬脂酸鈣、硬脂酸鎂、油酸鈣、油酸鎂、烯基丁二酸鈣、烯基丁二酸鎂、松香酸鈣或松香酸鎂,較佳為可列舉硬脂酸鈣、硬脂酸鎂等。另外,於玻璃填充劑(B)中,採用非晶結構的二氧化矽有時於骨架中包含鈣、鎂、或/及鋁作為離子,但矽酸的pKa為3以上,於本發明中相當於弱酸。 In the present invention, the term "weak acid" refers to a pKa (-logKa) of 3 or more. For example, fatty acids can be cited. As the salt of calcium or magnesium and a weak acid, calcium palmitate, magnesium palmitate, calcium stearate, magnesium stearate, calcium oleate, magnesium oleate, calcium alkenyl succinate, magnesium alkenyl succinate can be cited , Calcium rosinate or magnesium rosinate, preferably calcium stearate, magnesium stearate and the like. In addition, in the glass filler (B), silicon dioxide with an amorphous structure sometimes contains calcium, magnesium, or/and aluminum as ions in the skeleton, but the pKa of silicic acid is 3 or more, which is equivalent in the present invention. Yu weak acid.
所述合計含量NB'ca+mg的值是藉由分別算出含有橡膠的接枝聚合體(C)中的鈣或鎂與弱酸的鹽的合計含量的鈣及鎂的換算的合計含量C'ca+mg、與源自玻璃填充劑(B)及含有橡膠的接枝聚合體(C)以外的成分的鈣及鎂與弱酸的鹽的合計含量的鈣及鎂的換算的合計含量NBC'ca+mg,並利用下式來算出。 The total content of NB 'ca + value in mg is calculated by the total content of C, respectively containing calcium and magnesium graft rubber polymer (C) in the total content of calcium or magnesium salt of a weak acid in terms of' ca +mg , and the total content of calcium and magnesium converted from the total content of calcium and magnesium derived from the glass filler (B) and the graft polymer containing rubber (C) and the total content of the weak acid salt NBC' ca+ mg and use the following formula to calculate.
NB'ca+mg=C'ca+mg+NBC'ca+mg‧‧‧(8) NB' ca+mg =C' ca+mg +NBC' ca+mg ‧‧‧(8)
所述C'ca+mg藉由下式來算出。 The C'ca+mg is calculated by the following formula.
C'ca+mg=Mc×(cq'cas×r'ca+cq'mgs×r'mg)‧‧‧(9) C'ca+mg =Mc×(cq' cas ×r' ca +cq' mgs ×r' mg )‧‧‧(9)
Mc:樹脂組成物的「主要三成分」100質量份中的含有橡膠 的接枝聚合體(C)的質量份 Mc: Rubber contained in 100 parts by mass of the "main three components" of the resin composition The mass parts of graft polymer (C)
cq'cas:含有橡膠的接枝聚合體(C)中的鈣與弱酸的鹽的濃度 cq' cas : The concentration of calcium and weak acid salt in the rubber-containing graft polymer (C)
cq'mgs:含有橡膠的接枝聚合體(C)中的鎂與弱酸的鹽的濃度 cq' mgs : the concentration of magnesium and weak acid salt in the graft polymer (C) containing rubber
r'ca:鈣與弱酸的鹽中的鈣濃度 r'ca : the concentration of calcium in the salt of calcium and weak acid
r'mg:鎂與弱酸的鹽中的鎂濃度。 r'mg : the concentration of magnesium in the salt of magnesium and weak acid.
所述NBC'ca+mg藉由下式來算出。 The NBC'ca+mg is calculated by the following formula.
NBC'ca+mg=(mnbc'cas×r'ca)+(mnbc'mgs×r'mg)‧‧(10) NBC' ca+mg =(mnbc' cas ×r' ca )+(mnbc' mgs ×r' mg )‧‧(10)
mnbc'cas:相對於樹脂組成物的「主要三成分」的合計100質量份的樹脂組成物中的玻璃填充劑(B)及含有橡膠的接枝聚合體(C)以外的鈣與弱酸的鹽的質量份 mnbc' cas : The glass filler (B) and the rubber-containing graft polymer (C) other than the calcium and weak acid salt in the resin composition of 100 parts by mass relative to the total "main three components" of the resin composition Parts by mass
mnbc'mgs:相對於樹脂組成物的「主要三成分」的合計100質量份的樹脂組成物中的玻璃填充劑(B)及含有橡膠的接枝聚合體(C)以外的鎂與弱酸的鹽的質量份 mnbc' mgs : The glass filler (B) and the rubber-containing graft polymer (C) other than the glass filler (B) in the resin composition with respect to the total 100 parts by mass of the "main three components" of the resin composition and a weak acid salt Parts by mass
r'ca:鈣與弱酸的鹽中的鈣濃度 r'ca : the concentration of calcium in the salt of calcium and weak acid
r'mg:鎂與弱酸的鹽中的鎂濃度。 r'mg : the concentration of magnesium in the salt of magnesium and weak acid.
含有橡膠的接枝聚合體中的鈣及鎂與弱酸的鹽可藉由在製造含有橡膠的接枝聚合體時,使用脂肪酸與鹼金屬的鹽作為乳化劑、且使用包含鹼土金屬(2族)的鹽(氯化鈣、乙酸鈣、硫 酸鎂、氯化鎂等)而獲得。於使用包含所述鹼土金屬(2族)的凝聚劑作為凝聚劑的凝聚的過程中,用作乳化劑的「鹼金屬與弱酸的鹽」變成「鹼土金屬與弱酸的鹽」。鹼土金屬與弱酸的鹽因水溶性低,故可使乳膠中的聚合物粒子凝聚。其結果,因含有橡膠的接枝聚合體(C)與水分離,故可回收含有橡膠的接枝聚合體(C)。若對凝聚物進行清洗並加以乾燥,則可獲得含有橡膠的接枝聚合體(C)的粉體。鈣及鎂與弱酸的鹽的含量可藉由脂肪酸系的乳化劑調配量或清洗水量等來調整。源自玻璃填充劑(B)或含有橡膠的接枝聚合體(C)以外的成分的鈣及鎂與弱酸的鹽的含量亦可藉由在樹脂組成物的成形時調配所述鈣或鎂與弱酸的鹽來調整。 The salts of calcium and magnesium and weak acids in the rubber-containing graft polymer can be obtained by using fatty acid and alkali metal salts as emulsifiers and alkaline earth metals (group 2) when manufacturing rubber-containing graft polymers. Of salt (calcium chloride, calcium acetate, sulfur Magnesium acid, magnesium chloride, etc.). In the process of agglomeration using the flocculant containing the alkaline earth metal (Group 2) as the flocculant, the "alkali metal and weak acid salt" used as an emulsifier becomes the "alkaline earth metal and weak acid salt". Salts of alkaline earth metals and weak acids have low water solubility and can aggregate polymer particles in latex. As a result, since the rubber-containing graft polymer (C) is separated from water, the rubber-containing graft polymer (C) can be recovered. If the agglomerate is washed and dried, a powder of the graft polymer (C) containing rubber can be obtained. The content of calcium and magnesium and weak acid salts can be adjusted by the amount of fatty acid emulsifiers or the amount of washing water. The content of calcium and magnesium and the salt of weak acid derived from components other than the glass filler (B) or the rubber-containing graft polymer (C) can also be determined by blending the calcium or magnesium with the weak acid during the molding of the resin composition Weak acid salt to adjust.
[鋁] [aluminum]
樹脂組成物中的鋁與強酸的鹽會使工程塑膠(A)與玻璃填充劑(B)的密接性下降、且促進樹脂組成物的成形時的熱劣化,另外,使成形體的高溫高濕下的耐水解性惡化。尤其源自含有橡膠的接枝聚合體(C)的鋁與強酸的鹽會顯著地使工程塑膠(A)與玻璃填充劑(B)的密接性下降。再者,於工程塑膠(A)與玻璃填充劑(B)中,基本上不含鋁與強酸的鹽。有時於玻璃填充劑(B)中包含鋁,具有非晶結構的二氧化矽於其骨架中包含鋁作為離子。因此,於玻璃填充劑(B)中,基本上不含鋁與強酸的鹽。 The salt of aluminum and strong acid in the resin composition reduces the adhesion between the engineering plastic (A) and the glass filler (B), and promotes thermal deterioration during the molding of the resin composition. In addition, it causes high temperature and high humidity in the molded body. The hydrolysis resistance deteriorates. In particular, the salt of aluminum and strong acid derived from the rubber-containing graft polymer (C) significantly reduces the adhesion between the engineering plastic (A) and the glass filler (B). Furthermore, in engineering plastics (A) and glass fillers (B), there are basically no aluminum and strong acid salts. The glass filler (B) may contain aluminum, and silicon dioxide having an amorphous structure contains aluminum as an ion in its skeleton. Therefore, in the glass filler (B), the salt of aluminum and strong acid is basically not contained.
[測定方法X] [Measurement method X]
於本發明的第一形態的樹脂組成物中,藉由所述測定方法X所測定的乾燥試樣100質量份中的鋁含量為0.0008質量份以下。 當該含量為0.0008質量份(8ppm)以下時,所述工程塑膠(A)與玻璃填充劑(B)的密接性的下降、或樹脂組成物的成形時的熱劣化或成形體的水解性不會成為問題,因此成形體的衝擊強度或彎曲特性(彈性係數、強度)優異。該鋁的含量較佳為0.0006質量份以下(6ppm以下),進而更佳為0.0002質量份以下(2ppm以下)。若該含量的值為0.0006質量份以下,則工程塑膠(A)與玻璃填充劑(B)的密接性更優異。 In the resin composition of the first aspect of the present invention, the aluminum content in 100 parts by mass of the dry sample measured by the above-mentioned measuring method X is 0.0008 parts by mass or less. When the content is 0.0008 parts by mass (8 ppm) or less, the adhesiveness of the engineering plastic (A) and the glass filler (B) decreases, or the resin composition is thermally deteriorated during molding, or the hydrolyzability of the molded body is not It becomes a problem, and therefore the impact strength and bending characteristics (elasticity, strength) of the molded body are excellent. The content of aluminum is preferably 0.0006 parts by mass or less (6 ppm or less), and more preferably 0.0002 parts by mass or less (2 ppm or less). If the value of the content is 0.0006 parts by mass or less, the adhesiveness of the engineering plastic (A) and the glass filler (B) is more excellent.
藉由測定利用「測定方法X」所獲得的氯仿可溶部分的鋁的含量,大致能夠以鋁換算來求出樹脂組成物的「樹脂二成分」中的鋁與強酸的鹽。其理由在於:鋁與弱酸的鹽難以溶解於氯仿中、及玻璃填充劑(B)難以溶解於氯仿中。藉由測定樹脂組成物中的氯仿可溶部分的鋁量,大致可測定源自鋁與強酸的鹽的鋁量。另外,玻璃填充劑(B)有時包含鋁,但於樹脂組成物中的氯仿可溶部分中,實質上不含源自玻璃填充劑(B)的鋁。 By measuring the aluminum content of the chloroform-soluble portion obtained by "Measuring Method X", the salt of aluminum and strong acid in the "resin two components" of the resin composition can be roughly calculated in terms of aluminum. The reason is that the salt of aluminum and a weak acid is difficult to dissolve in chloroform, and the glass filler (B) is difficult to dissolve in chloroform. By measuring the amount of aluminum in the chloroform-soluble portion of the resin composition, the amount of aluminum derived from the salt of aluminum and a strong acid can be roughly measured. In addition, the glass filler (B) may contain aluminum, but the chloroform-soluble portion in the resin composition does not substantially contain aluminum derived from the glass filler (B).
若藉由測定方法X所獲得的「乾燥試樣」100質量份中的鋁的含量為0.0008質量份以下(8ppm以下),則本發明的樹脂組成物100質量份中的鋁與強酸的鹽以鋁換算量計低於0.0008質量份(少於8ppm)。為了減少藉由測定方法X所測定的乾燥試樣100質量份中的鋁的含量及源自含有橡膠的接枝聚合體(C)的鋁與強酸的鹽的含量,較佳為對含有橡膠的接枝聚合體(C)進行噴霧回收。當對含有橡膠的接枝聚合體(C)進行凝聚並加以回收時,較佳為使用包含鹼土金屬(2族)或鋁等土類金屬(13族)的鹽 (氯化鈣、乙酸鈣、硫酸鎂、氯化鎂、硫酸鋁等)作為凝聚劑,於清洗時使用大量的水,並有效地利用離心分離機等來充分地去除漿料中的水分。 If the content of aluminum in 100 parts by mass of the "dry sample" obtained by the measurement method X is 0.0008 parts by mass or less (8 ppm or less), the salt of aluminum and strong acid in 100 parts by mass of the resin composition of the present invention is The aluminum conversion amount is less than 0.0008 parts by mass (less than 8 ppm). In order to reduce the content of aluminum in 100 parts by mass of the dry sample measured by the measurement method X and the content of the salt of aluminum and strong acid derived from the rubber-containing graft polymer (C), it is preferable to The graft polymer (C) is sprayed and recovered. When the rubber-containing graft polymer (C) is aggregated and recovered, it is preferable to use a salt containing alkaline earth metals (group 2) or earth metals (group 13) such as alumina (Calcium Chloride, Calcium Acetate, Magnesium Sulfate, Magnesium Chloride, Aluminum Sulfate, etc.) As a coagulant, a large amount of water is used for cleaning, and a centrifuge is effectively used to fully remove the water in the slurry.
[鋁與強酸的鹽] [Aluminum and strong acid salt]
另外,於本發明的第二形態的樹脂組成物中,相對於樹脂組成物的「主要三成分」的合計100質量份,該樹脂組成物中的鋁與強酸的鹽的合計含量的鋁換算的含量「Tal」為0.0008質量份以下。藉由分別算出含有橡膠的接枝聚合體(C)中的鋁與強酸的鹽的含量的鋁的換算的含量Cal、與含有橡膠的接枝聚合體(C)以外的鋁與強酸的鹽的鋁的換算量NCal,並利用下式來算出Tal。 In addition, in the resin composition of the second aspect of the present invention, the total content of aluminum and the salt of a strong acid in the resin composition is calculated as aluminum in terms of the total content of aluminum and the salt of a strong acid relative to 100 parts by mass of the total "three main components" of the resin composition The content "T al "is 0.0008 parts by mass or less. By calculating the content of aluminum and the salt of strong acid in the graft polymer containing rubber (C), the converted content of aluminum C al , and the salt of aluminum and strong acid other than the graft polymer containing rubber (C) The conversion amount of aluminum is NC al , and T al is calculated using the following formula.
Tal=Cal+NCal‧‧‧(11) T al =C al +NC al ‧‧‧(11)
所述Cal藉由下式來算出。 The Cal is calculated by the following formula.
Cal=Mc×cqal×ral‧‧‧(12) C al =Mc×cq al ×r al ‧‧‧(12)
Mc:樹脂組成物的「主要三成分」100質量份中的含有橡膠的接枝聚合體(C)的質量份 Mc: parts by mass of the graft polymer (C) containing rubber in 100 parts by mass of the "main three components" of the resin composition
cqals:含有橡膠的接枝聚合體(C)中的鋁與強酸的鹽的濃度 cq als :The concentration of the salt of aluminum and strong acid in the graft polymer (C) containing rubber
ral:鋁與強酸的鹽中的鋁濃度。 r al : Aluminum concentration in the salt of aluminum and strong acid.
所述NCal藉由下式來算出。 The NC al is calculated by the following formula.
NCal=mncals×ral‧‧‧(13) NC al =mnc als ×r al ‧‧‧(13)
mncals:相對於樹脂組成物的「主要三成分」的合計100質量份的源自含有橡膠的接枝聚合體(C)以外的成分的鋁與強酸的鹽的質量份 mnc als : The weight parts of the salt of aluminum and strong acid derived from components other than the graft polymer (C) containing rubber relative to the total 100 parts by weight of the "main three components" of the resin composition
ral:鋁與強酸的鹽中的鋁濃度。 r al : Aluminum concentration in the salt of aluminum and strong acid.
若所述鋁換算含量Tal為0.0008質量份以下(8ppm以下),則工程塑膠(A)與玻璃填充劑(B)的密接性、樹脂組成物的成形時的熱劣化或成形體的水解性不會成為問題,因此成形體的衝擊強度或彎曲特性(彈性係數及強度)優異。該鋁換算含量Tal更佳為0.0006質量份以下(6ppm以下),進而更佳為0.0002質量份以下(2ppm以下)。 If the aluminum conversion content T al is 0.0008 parts by mass or less (8 ppm or less), the adhesiveness of the engineering plastic (A) and the glass filler (B), the thermal deterioration of the resin composition during molding, or the hydrolysis of the molded body There is no problem, and therefore the impact strength and bending characteristics (elasticity and strength) of the molded body are excellent. The content T al in terms of aluminum is more preferably 0.0006 parts by mass or less (6 ppm or less), and still more preferably 0.0002 parts by mass or less (2 ppm or less).
[其他添加劑等] [Other additives, etc.]
除所述材料以外,本發明的樹脂組成物可於無損本發明的目的的範圍內,含有眾所周知的各種添加劑,例如穩定劑、阻燃劑、阻燃助劑、水解抑制劑、抗靜電劑、發泡劑、染料、顏料等。 In addition to the aforementioned materials, the resin composition of the present invention may contain various well-known additives such as stabilizers, flame retardants, flame retardant additives, hydrolysis inhibitors, antistatic agents, Foaming agents, dyes, pigments, etc.
[調配方法] [Allocation method]
作為製備本發明的樹脂組成物時的各材料的調配方法,可列舉公知的摻合方法,並無特別限定。例如可列舉:利用轉筒、V型摻合機、高速混合器(super mixer)、諾塔混合器(nauta mixer)、班布里混合器(banbury mixer)、混練輥、擠出機等進行混合、混 練的方法。另外,例如可列舉:在溶解於二氯甲烷等工程塑膠(A)與含有橡膠的接枝聚合體(C)的共同的良溶媒中的狀態下進行混合的溶液摻合方法等。 As a compounding method of each material when preparing the resin composition of this invention, a well-known blending method can be mentioned, and it does not specifically limit. Examples include: mixing using a rotating drum, a V-type blender, a super mixer, a nauta mixer, a banbury mixer, a kneading roll, an extruder, etc. ,mix Method of practice. In addition, for example, a solution blending method in which the engineering plastic (A) such as methylene chloride and the rubber-containing graft polymer (C) are dissolved in a common good solvent and the like is mixed.
[成形體] [Formed body]
本發明的樹脂組成物可藉由公知的成形方法而製成所期望的形狀的成形體。樹脂組成物可直接藉由擠出成形法、射出成形法、壓縮成形法等來成形,或利用熔融擠出機暫時製成顆粒後,藉由擠出成形法、射出成形法、壓縮成形法等來成形。成形體並無特別限定,可列舉:汽車領域或家電領域等中的各種構件(電視機殼(TV frame)、個人電腦的框體、車輛用內裝構件(儀表板等)、車輛用外裝構件(擋泥板、支柱等)等)。 The resin composition of the present invention can be formed into a molded body of a desired shape by a known molding method. The resin composition can be directly molded by extrusion molding, injection molding, compression molding, etc., or after being temporarily formed into pellets by a melt extruder, by extrusion molding, injection molding, compression molding, etc. To take shape. The molded body is not particularly limited, and examples include various components (TV frames, personal computer housings, vehicle interior components (instrument panels, etc.), vehicle exteriors in the automotive field or home appliance field, etc. Components (fenders, pillars, etc.), etc.).
[實施例] [Example]
以下,藉由製造例及實施例來更詳細地說明本發明。製造例1~製造例12為橡膠狀聚合體及含有橡膠的接枝聚合體(C)等的製造例。再者,「份」表示「質量份」,「%」表示「質量%」。 Hereinafter, the present invention will be explained in more detail through manufacturing examples and examples. Production example 1 to production example 12 are production examples of a rubber-like polymer, a rubber-containing graft polymer (C), and the like. Furthermore, "parts" means "parts by mass", and "%" means "mass%".
<製造例1> <Manufacturing Example 1>
將八甲基環四矽氧烷97.5份、γ-甲基丙烯醯氧基丙基二甲氧基甲基矽烷0.5份及四乙氧基矽烷2.0份混合而獲得矽氧烷混合物100份。向其中添加使十二基苯磺酸鈉(DBSNa)0.67份溶解於去離子水180份中而成的溶液,並利用均質混合器以10,000rpm攪拌5分鐘。繼而,於20MPa的壓力下在均質機中通過2次,而獲得矽氧烷乳膠。 97.5 parts of octamethylcyclotetrasiloxane, 0.5 part of γ-methacryloxypropyldimethoxymethylsilane, and 2.0 parts of tetraethoxysilane were mixed to obtain 100 parts of a silicone mixture. A solution prepared by dissolving 0.67 parts of sodium dodecylbenzene sulfonate (DBSNa) in 180 parts of deionized water was added thereto, and the mixture was stirred at 10,000 rpm for 5 minutes with a homomixer. Then, it passes through a homogenizer twice under a pressure of 20 MPa to obtain a silicone emulsion.
將所述矽氧烷乳膠投入至具備冷卻管、溫度計及攪拌裝置的可分離式燒瓶內,進而添加作為觸媒的十二基苯磺酸0.5份,而獲得矽氧烷乳膠組成物。繼而,於將所獲得的矽氧烷乳膠組成物加熱至80℃的狀態下維持8小時而使有機矽氧烷進行聚合。聚合後,對包含聚合產物的乳膠進行冷卻,然後使用5%氫氧化鈉水溶液中和至pH值為7.0,而獲得POSi(S-1)的乳膠。POSi(S-1)的乳膠的固體成分為35.5%,聚合體的質量平均粒徑為220nm。 The silicone latex was put into a separable flask equipped with a cooling tube, a thermometer, and a stirring device, and 0.5 part of dodecylbenzenesulfonic acid as a catalyst was further added to obtain a silicone latex composition. Then, the obtained silicone latex composition was heated to 80° C. and maintained for 8 hours to polymerize the organosiloxane. After the polymerization, the latex containing the polymerization product is cooled, and then neutralized to a pH of 7.0 with a 5% sodium hydroxide aqueous solution, to obtain a POSi (S-1) latex. The solid content of POSi (S-1) latex is 35.5%, and the mass average particle size of the polymer is 220 nm.
<製造例2> <Manufacturing Example 2>
將製造例1中所獲得的POSi(S-1)的乳膠28.5份(作為加入單體成分為10份)投入至具備冷卻管、溫度計、氮氣導入管及攪拌裝置的可分離式燒瓶內,進而添加表1中所示的「成分1」,並進行混合。藉由使氮氣氣流於該可分離式燒瓶內通過來進行燒瓶內環境的氮氣置換,並將液溫昇溫至70℃為止。於液溫變成70℃的時間點添加表1中所示的「成分2」的混合液,並使聚合開始。其後,將液溫70℃保持10分鐘。 Put 28.5 parts of POSi(S-1) latex (10 parts as the added monomer component) obtained in Production Example 1 into a separable flask equipped with a cooling tube, a thermometer, a nitrogen introduction tube, and a stirring device, and then "Ingredient 1" shown in Table 1 was added and mixed. The atmosphere in the flask was replaced with nitrogen by passing a nitrogen stream through the separable flask, and the liquid temperature was raised to 70°C. At the time when the liquid temperature became 70°C, the mixed liquid of "Component 2" shown in Table 1 was added, and the polymerization was started. Thereafter, the liquid temperature was maintained at 70°C for 10 minutes.
進而,使表1中所示的「成分3」的混合液進行強制乳化,並歷時150分鐘滴加至可分離式燒瓶內。其後保持60分鐘,並添加表1中所示的「成分4」的混合液,進而歷時60分鐘將表1中所示的「成分5」的混合液滴加至可分離式燒瓶內,並保持90分鐘。如此,獲得含有矽酮系聚合體的乙烯基聚合體的乳膠。使用噴霧器式噴霧乾燥機(大川原化工機(股份)製造,商品名;L-8型噴霧乾燥器),以乾燥用加熱氣體的入口溫度140℃及出口 溫度65℃對所獲得的乳膠進行噴霧乾燥,而獲得含有橡膠的接枝聚合體(Csa-1)的粉體。 Furthermore, the mixed liquid of the "component 3" shown in Table 1 was forcedly emulsified, and was dropped into the separable flask over 150 minutes. After that, the mixture of "component 4" shown in Table 1 was added for 60 minutes, and the mixed liquid of "component 5" shown in Table 1 was added dropwise to the separable flask over 60 minutes, and Keep it for 90 minutes. In this way, a latex of a vinyl polymer containing a silicone polymer was obtained. Use a spray dryer (manufactured by Ogawara Chemical Industry Co., Ltd., trade name; L-8 spray dryer), with the inlet temperature of the heating gas for drying at 140°C and outlet The obtained latex was spray-dried at a temperature of 65°C to obtain a rubber-containing graft polymer (Csa-1) powder.
<製造例3> <Manufacturing Example 3>
將調配有表2中所示的「成分1」的水溶液設定為溫度為30℃,將製造例2中所獲得的乳膠投入至該水溶液中,並將液溫昇溫至80℃,然後進行鹽析。對凝聚聚合物進行回收,浸漬於去離子水1500份中,並進行脫水,將該步驟重複2次,然後於溫度80℃下乾燥一晚,而獲得含有橡膠的接枝聚合體(Csa-2)的粉體。 The aqueous solution prepared with "Component 1" shown in Table 2 was set to a temperature of 30°C, the latex obtained in Production Example 2 was put into the aqueous solution, and the liquid temperature was raised to 80°C, and then salting out . The agglomerated polymer was recovered, immersed in 1500 parts of deionized water, and dehydrated. This step was repeated twice, and then dried at a temperature of 80°C overnight to obtain a rubber-containing graft polymer (Csa-2 ) Of the powder.
<製造例4> <Manufacturing Example 4>
將製造例1中所獲得的POSi(S-1)的乳膠28.5份(作為加入單體成分為10份)投入至具備冷卻管、溫度計、氮氣導入管及攪拌裝置的可分離式燒瓶內,進而添加表3中所示的「成分1」,並進行混合。藉由使氮氣氣流於該可分離式燒瓶內通過來進行燒瓶內環境的氮氣置換,並將液溫昇溫至50℃為止。於液溫變成50℃的時間點添加表3中所示的「成分2」的混合液,並使聚合開始。其後,將液溫65℃保持30分鐘。進而,歷時30分鐘將表3中所示的「成分3」的混合液滴加至可分離式燒瓶內,並保持60分鐘。如此獲得乳膠。 Put 28.5 parts of POSi(S-1) latex (10 parts as the added monomer component) obtained in Production Example 1 into a separable flask equipped with a cooling tube, a thermometer, a nitrogen introduction tube, and a stirring device, and then "Ingredient 1" shown in Table 3 was added and mixed. The atmosphere in the flask was replaced with nitrogen by passing a stream of nitrogen through the separable flask, and the liquid temperature was raised to 50°C. At the time when the liquid temperature became 50°C, the mixed liquid of "Component 2" shown in Table 3 was added, and the polymerization was started. Thereafter, the liquid temperature was maintained at 65°C for 30 minutes. Furthermore, the mixed liquid of "component 3" shown in Table 3 was dropped into the separable flask over 30 minutes, and kept for 60 minutes. In this way, latex is obtained.
將調配有表3中所示的「成分4」的水溶液設定為溫度為30℃,將所述乳膠投入至該水溶液中,並將液溫昇溫至80℃,然後進行鹽析。對凝聚聚合物進行回收,並於溫度80℃下乾燥一晚,而獲得含有橡膠的接枝聚合體(Csa-3)的粉體。 The temperature of the aqueous solution prepared with "component 4" shown in Table 3 was set to 30°C, the latex was poured into the aqueous solution, the liquid temperature was raised to 80°C, and then salting out was performed. The agglomerated polymer was recovered and dried at a temperature of 80°C overnight to obtain a rubber-containing graft polymer (Csa-3) powder.
<製造例5> <Manufacturing Example 5>
將表4中所示的「成分1」加入至具備攪拌機及回流冷卻管的反應容器內,於溫度70℃下加熱攪拌1.5小時來進行聚合。繼而,歷時1小時將包含表4中所示的「成分2」的混合物滴加至反應容器內,其後繼續加熱攪拌1小時,而獲得含有酸基的共聚物乳膠。 The "component 1" shown in Table 4 was added to a reaction vessel equipped with a stirrer and a reflux cooling tube, and heated and stirred at a temperature of 70°C for 1.5 hours to perform polymerization. Then, the mixture containing the "component 2" shown in Table 4 was dropped into the reaction vessel over 1 hour, and then heating and stirring were continued for 1 hour to obtain an acid group-containing copolymer latex.
<製造例6> <Manufacturing Example 6>
於溫度80℃下使表5中所示的「成分1」溶解。繼而,將表5中所示的「成分2」的水溶液投入至所述溶液中來進行強制乳化,而製備穩定劑的乳液。 The "component 1" shown in Table 5 was dissolved at a temperature of 80°C. Then, the aqueous solution of "component 2" shown in Table 5 was poured into the solution to be forcedly emulsified, and an emulsion of a stabilizer was prepared.
<製造例7> <Manufacturing Example 7>
(1)橡膠狀聚合體的乳膠(R-1)的製造 (1) Production of rubber-like polymer latex (R-1)
將作為第一單量體混合液的表6中所示的「成分1」加入至 容量70L的高壓釜內,並進行昇溫,於液溫變成43℃的時間點,添加表6中所示的「成分2」的氧化還原系起始劑來開始反應,其後,進而將液溫昇溫至65℃為止。自聚合開始起3小時後添加表6中所示的「成分3」的聚合起始劑,自其1小時後歷時8小時將「成分4」的第二單量體混合液、「成分5」的乳化劑水溶液、「成分6」的聚合起始劑連續地滴加至高壓釜內。自聚合開始起進行4小時反應,而獲得橡膠狀聚合體的乳膠(R-1)。該乳膠中的聚合體粒子的質量平均粒徑為170nm,dw/dn=1.2。 Add "Ingredient 1" shown in Table 6 as the first single-body mixture to In an autoclave with a volume of 70L, the temperature was increased. At the time when the liquid temperature became 43°C, the redox initiator of "Component 2" shown in Table 6 was added to start the reaction, and then the liquid temperature The temperature is raised to 65°C. After 3 hours from the start of polymerization, the polymerization initiator of "Component 3" shown in Table 6 was added, and the second monomer mixture of "Component 4" and "Component 5" were added over 8 hours after 1 hour. The aqueous emulsifier solution and the polymerization initiator of "Component 6" were continuously added dropwise into the autoclave. The reaction was carried out for 4 hours from the start of polymerization to obtain a rubber-like polymer latex (R-1). The mass average particle diameter of the polymer particles in the latex is 170 nm, and dw/dn=1.2.
(2)含有橡膠的接枝聚合體的乳膠(Rgr-1)的製造 (2) Manufacturing of latex (R gr -1) of graft polymer containing rubber
將乳膠(R-1)219份(作為加入單體成分為77.5份)加入至具備攪拌機及回流冷卻管的反應容器內,並添加表7中所示的「成分1」。繼而,將反應容器內的液溫昇溫至55℃,並添加包含表7中所示的「成分2」的水溶液,繼而,歷時60分鐘將表7中所示的「成分3」的混合物滴加至反應容器內,進而繼續加熱攪拌60分鐘。繼而,歷時60分鐘將表7中所示的「成分4」的混合物滴加至反應容器內,進而繼續加熱攪拌60分鐘。如此,使乙烯基單量體對於橡膠狀聚合體進行接枝聚合,而獲得含有橡膠的接枝聚 合體的乳膠(Rgr-1)。 219 parts of latex (R-1) (77.5 parts as the added monomer component) were added to a reaction vessel equipped with a stirrer and a reflux cooling tube, and "component 1" shown in Table 7 was added. Then, the temperature of the liquid in the reaction vessel was raised to 55°C, and an aqueous solution containing "component 2" shown in Table 7 was added, and then the mixture of "component 3" shown in Table 7 was added dropwise over 60 minutes Into the reaction vessel, continue to heat and stir for 60 minutes. Then, the mixture of "component 4" shown in Table 7 was dropped into the reaction vessel over 60 minutes, and heating and stirring were continued for 60 minutes. In this way, the vinyl monomer is graft-polymerized to the rubber-like polymer to obtain a rubber-containing graft polymer latex (R gr -1).
<製造例8> <Manufacturing Example 8>
於製造例7中所獲得的含有橡膠的接枝聚合體的乳膠(Rgr-1)243.9份中調配製造例6的穩定劑的乳液2.2份,並進行混合。繼而,使用噴霧器式噴霧乾燥機(大川原化工機(股份)製造,商品名;L-8型噴霧乾燥器),以乾燥用加熱氣體的入口溫度140℃及出口溫度65℃進行噴霧乾燥,而獲得含有橡膠的接枝聚合體(Cba-4)的粉體。 To 243.9 parts of the rubber-containing graft polymer latex (R gr -1) obtained in Production Example 7, 2.2 parts of the stabilizer emulsion of Production Example 6 was blended and mixed. Then, using a spray dryer (manufactured by Ogawara Chemical Industry Co., Ltd., trade name; L-8 type spray dryer), spray drying is performed at an inlet temperature of 140°C and an outlet temperature of 65°C of the heating gas for drying to obtain Graft polymer (Cba-4) powder containing rubber.
<製造例9> <Manufacturing Example 9>
於製造例7中所獲得的含有橡膠的接枝聚合體的乳膠(Rgr-1)243.9份中調配製造例6的穩定劑的乳液2.2份,並進行混合。進而,調配烷基二苯基醚二磺酸鈉(SS-L)0.5份。繼而,使用噴霧器式噴霧乾燥機(大川原化工機(股份)製造,商品名;L-8型噴霧乾燥器),以乾燥用加熱氣體的入口溫度140℃及出口溫度65℃ 進行噴霧乾燥,而獲得含有橡膠的接枝聚合體(Cba-5)的粉體。 To 243.9 parts of the rubber-containing graft polymer latex (R gr -1) obtained in Production Example 7, 2.2 parts of the stabilizer emulsion of Production Example 6 was blended and mixed. Furthermore, 0.5 part of sodium alkyl diphenyl ether disulfonate (SS-L) was prepared. Then, using a spray dryer (manufactured by Ogawara Chemical Industry Co., Ltd., trade name; L-8 spray dryer), spray drying is performed at an inlet temperature of 140°C and an outlet temperature of 65°C of the heating gas for drying, and the obtained Graft polymer (Cba-5) powder containing rubber.
<製造例10> <Manufacturing Example 10>
(1)橡膠狀聚合體的乳膠(R-2)的製造 (1) Manufacture of rubber-like polymer latex (R-2)
將表8中所示的「成分1」添加至具備攪拌機的高壓釜內,並對高壓釜內的環境進行氮氣置換。繼而,添加表8中所示的「成分2」後進行密封,並將液溫昇溫至50℃。繼而,添加包含表8中所示的「成分3」的氧化還原觸媒水溶液後,於溫度55℃下進行8小時聚合,藉此獲得橡膠狀聚合體的乳膠(R-2)。該乳膠中的聚合體粒子的質量平均粒徑為100nm,固體成分為32.1%。 "Component 1" shown in Table 8 was added to the autoclave equipped with a stirrer, and the atmosphere in the autoclave was replaced with nitrogen. Then, the "component 2" shown in Table 8 was added and sealed, and the liquid temperature was raised to 50°C. Then, after adding an aqueous redox catalyst solution containing "Component 3" shown in Table 8, polymerization was performed at a temperature of 55°C for 8 hours, thereby obtaining a rubbery polymer latex (R-2). The mass average particle diameter of the polymer particles in the latex was 100 nm, and the solid content was 32.1%.
(2)含有橡膠的接枝聚合體的乳膠(Rgr-2)的製造 (2) Manufacturing of latex (R gr -2) of graft polymer containing rubber
將乳膠(R-2)242份加入至具備攪拌機及回流冷卻管的反應容器內,並將液溫昇溫至40℃。繼而,添加表9中所示的「成分1」,並攪拌30分鐘。其後,調配表9中所示的「成分2」的水溶液。所獲得的乳膠中的聚合體粒子的質量平均粒徑為250nm。 242 parts of latex (R-2) was added to the reaction container equipped with a stirrer and a reflux cooling tube, and the liquid temperature was raised to 40°C. Then, "ingredient 1" shown in Table 9 was added and stirred for 30 minutes. Thereafter, the aqueous solution of "component 2" shown in Table 9 was prepared. The mass average particle diameter of the polymer particles in the obtained latex was 250 nm.
繼而,將反應容器內的液溫昇溫至55℃,並添加表9中所示的「成分3」的水溶液,繼而,歷時50分鐘滴加表9中所示的「成分4」的混合物,進而繼續加熱攪拌60分鐘。繼而,歷時60分鐘滴加表9中所示的「成分5」的混合物,進而繼續加熱攪拌60分鐘。繼而,歷時10分鐘滴加表9中所示的「成分6」的混合物,進而繼續加熱攪拌60分鐘。於滴加後15分鐘的時間點,添加包含表9中所示的「成分7」的氧化還原觸媒水溶液,並添加表9中所示的「成分8」來進行接枝聚合。如此,使乙烯基單量體對於橡膠狀聚合體進行接枝聚合,而獲得含有橡膠的接枝聚合體的乳膠(Rgr-2)。 Then, the temperature of the liquid in the reaction vessel was raised to 55°C, the aqueous solution of "component 3" shown in Table 9 was added, and then the mixture of "component 4" shown in Table 9 was added dropwise over 50 minutes, and then Continue heating and stirring for 60 minutes. Then, the mixture of "component 5" shown in Table 9 was added dropwise over 60 minutes, and heating and stirring were continued for 60 minutes. Then, the mixture of "ingredient 6" shown in Table 9 was dropped over 10 minutes, and heating and stirring were continued for 60 minutes. At a time point of 15 minutes after the dripping, an aqueous redox catalyst solution containing "component 7" shown in Table 9 was added, and "component 8" shown in Table 9 was added to perform graft polymerization. In this way, the vinyl monomer is graft-polymerized to the rubber-like polymer to obtain a rubber-containing graft polymer latex (R gr -2).
於該乳膠(Rgr-2)285.9份中調配製造例6的穩定劑的乳液2.2份並進行混合。 2.2 parts of the emulsion of the stabilizer of Production Example 6 was blended and mixed with 285.9 parts of the latex (R gr -2).
調配表10中所示的「成分1」,而製備溫度為35℃的水溶液。將所述乳膠投入至該水溶液中,並將液溫昇溫至75℃來進行酸凝固。其後,投入10%的氫氧化鈉水溶液,並將漿料中的pH值設定為3。對該漿料進行冷卻,回收凝聚物,浸漬於去離子水1500份中,並進行脫水,將該步驟重複2次,然後於溫度80℃下乾燥一晚。如此獲得含有橡膠的接枝聚合體(Cba-6)的粉體。 "Component 1" shown in Table 10 was blended to prepare an aqueous solution with a temperature of 35°C. The latex was put into this aqueous solution, and the liquid temperature was raised to 75°C to perform acid coagulation. After that, a 10% sodium hydroxide aqueous solution was added, and the pH value in the slurry was set to 3. The slurry was cooled, the agglomerate was recovered, immersed in 1500 parts of deionized water, and dehydrated. This step was repeated twice, and then dried at a temperature of 80°C overnight. Thus, a powder of a rubber-containing graft polymer (Cba-6) was obtained.
<製造例11> <Manufacturing Example 11>
除使用表11中所示的「成分4'」來代替表3中所示的「成分4」以外,以與製造例4相同的方式獲得含有橡膠的接枝聚合體(Csa-7)的粉體。 Except for using "Component 4'" shown in Table 11 instead of "Component 4" shown in Table 3, a powder of a graft polymer containing rubber (Csa-7) was obtained in the same manner as in Production Example 4 body.
<製造例12> <Manufacturing Example 12>
除使用表12中所示的「成分4"」來代替表3中所示的「成分4」以外,以與製造例4相同的方式獲得含有橡膠的接枝聚合體(Csa-8)的粉體。 Except for using "Component 4" shown in Table 12 instead of "Component 4" shown in Table 3, a powder of a graft polymer containing rubber (Csa-8) was obtained in the same manner as in Production Example 4 body.
<評價方法> <Evaluation method>
[測定1]含有橡膠的接枝聚合體中的鈉離子量、鉀離子量、鋁離子量、鎂離子量、鈣離子量的定量 [Measurement 1] Quantification of the amount of sodium ion, potassium ion, aluminum ion, magnesium ion, and calcium ion in graft polymer containing rubber
使用各製造例中所獲得的含有橡膠的接枝聚合體作為試樣,並藉由以下的方法來進行測定。 The rubber-containing graft polymer obtained in each production example was used as a sample, and the measurement was performed by the following method.
[1]檢液(test liquid)的製備 [1] Preparation of test liquid
於分解容器內秤取試樣0.25g,向該容器內添加硝酸8ml並利用微波來使試樣分解(濕式分解)。對試樣液進行冷卻後,向該容器內放入氫氟酸2ml,再次利用微波進行處理,並藉由蒸餾水來定容成50ml而製成檢液。 A sample of 0.25 g was weighed in the decomposition container, 8 ml of nitric acid was added to the container, and the sample was decomposed by microwave (wet decomposition). After cooling the sample solution, put 2ml of hydrofluoric acid into the container, and then treat it with microwave again, and distilled water to make the volume to 50ml to prepare the test solution.
[2]各離子濃度的定量 [2] Quantification of each ion concentration
使用感應耦合電漿(Inductively Coupled Plasma,ICP)發光分析裝置(IRIS Interpid II XSP:賽默(Thermo)公司製造),對該檢液的鈉、鉀、鋁、鎂、鈣的離子量進行定量(單位為ppm)。將結果彙總於表13中。 Using an Inductively Coupled Plasma (ICP) luminescence analyzer (IRIS Interpid II XSP: manufactured by Thermo (Thermo)), the amount of sodium, potassium, aluminum, magnesium, and calcium in the test solution was quantified ( The unit is ppm). The results are summarized in Table 13.
[測定2]含有橡膠的接枝聚合體中的脂肪酸的量的測定 [Measurement 2] Measurement of the amount of fatty acid in the graft polymer containing rubber
使用各製造例中所獲得的含有橡膠的接枝聚合體作為試樣,並藉由以下的方法來進行測定。 The rubber-containing graft polymer obtained in each production example was used as a sample, and the measurement was performed by the following method.
[1]試樣液的製備 [1] Preparation of sample solution
向容器內放入試樣0.2g及0.1%三氟乙酸(甲苯溶液)10ml,並於溫度80℃下攪拌60分鐘,而使試樣溶解。繼而,向該容器內添加三氟化硼甲醇1g,並以溫度80℃、30分鐘的條件進行甲酯化處理。向該容器內添加蒸餾水10ml與己烷10ml來進行二層分離,並將己烷層作為試樣液。 Put 0.2 g of the sample and 10 ml of 0.1% trifluoroacetic acid (toluene solution) in the container, and stir at 80°C for 60 minutes to dissolve the sample. Then, 1 g of boron trifluoride methanol was added to the container, and the methyl esterification treatment was performed under the conditions of a temperature of 80°C for 30 minutes. 10 ml of distilled water and 10 ml of hexane were added to the container to perform two-layer separation, and the hexane layer was used as a sample liquid.
[2]脂肪酸的量的測定 [2] Determination of the amount of fatty acids
將試樣液1μl注入至氣相層析儀內,測定棕櫚酸、油酸、硬脂酸、烯基丁二酸二鉀、松香酸的量。將測定值換算成單位試樣質量的濃度。將結果彙總於表13中。 1 μl of the sample solution was injected into the gas chromatograph, and the amounts of palmitic acid, oleic acid, stearic acid, dipotassium alkenyl succinate, and abietic acid were measured. Convert the measured value to the concentration per unit mass of the sample. The results are summarized in Table 13.
[測定3]含有橡膠的接枝聚合體中的丙酮不溶部分的測定 [Measurement 3] Measurement of the acetone-insoluble part of the graft polymer containing rubber
[1]乾燥試樣的製備 [1] Preparation of dry samples
製備包含含有橡膠的接枝聚合體1質量%、丙酮99質量%的溶液,並進行以下(1)~(4)的操作而獲得「乾燥試樣」。 A solution containing 1% by mass of a rubber-containing graft polymer and 99% by mass of acetone was prepared, and the following operations (1) to (4) were performed to obtain a "dry sample".
(1)將所述溶液供於離心分離機並以20000rpm進行30分鐘離心分離。 (1) The solution was supplied to a centrifuge and centrifuged at 20000 rpm for 30 minutes.
(2)對上清液進行萃取,並放入至燒瓶內。 (2) Extract the supernatant and put it into the flask.
(3)將燒瓶設置於溫度為56℃的恆溫槽中,並利用蒸發器餾去揮發成分。 (3) Set the flask in a constant temperature bath with a temperature of 56°C, and use an evaporator to distill off volatile components.
(4)於溫度120℃下對燒瓶內的殘存物進行3小時乾燥而獲得「乾燥試樣」。 (4) Dry the residue in the flask at a temperature of 120°C for 3 hours to obtain a "dry sample".
[2]丙酮可溶部分的算出 [2] Calculation of acetone soluble part
因所述「乾燥試樣」為丙酮可溶部分,故藉由「100-丙酮可溶部分」來算出丙酮不溶部分。將結果彙總於表13中。 Since the "dry sample" is the acetone soluble part, the acetone insoluble part is calculated from the "100-acetone soluble part". The results are summarized in Table 13.
[測定4]樹脂組成物中的鋁離子量、鎂離子量、鈣離子量的定量([測定方法X]) [Measurement 4] Quantification of the amount of aluminum ion, magnesium ion, and calcium ion in the resin composition ([Measurement Method X])
[1]乾燥試樣的製備 [1] Preparation of dry samples
使用實施例6、實施例9、實施例12及比較例8中所獲得的樹脂組成物作為試樣,製備包含各樹脂組成物5質量%及氯仿95質量%的溶液,並進行以下(1)~(4)的操作而獲得「乾燥試樣」。 Using the resin compositions obtained in Example 6, Example 9, Example 12, and Comparative Example 8 as samples, a solution containing 5% by mass of each resin composition and 95% by mass of chloroform was prepared, and the following (1) The operation of ~(4) obtains a "dry sample".
(1)將所述溶液供於離心分離機並以5000rpm進行30分鐘 離心分離。 (1) Supply the solution to a centrifuge and run at 5000 rpm for 30 minutes Centrifugal separation.
(2)對上清液進行萃取,並放入至燒瓶內。 (2) Extract the supernatant and put it into the flask.
(3)將該燒瓶設置於溫度為68℃的恆溫槽中,並利用蒸發器自該液中餾去揮發成分。 (3) The flask was set in a constant temperature bath at 68°C, and volatile components were distilled off from the liquid using an evaporator.
(4)於溫度120℃下對該燒瓶內的殘存物進行3小時乾燥而獲得「乾燥試樣」。 (4) Dry the residue in the flask at a temperature of 120°C for 3 hours to obtain a "dry sample".
[2]將藉由所述操作而獲得的乾燥試樣用作試樣,以與測定1相同的方式進行鋁離子濃度、鎂離子濃度、鈣離子濃度的定量,並將結果彙總於表16中。 [2] Using the dried sample obtained by the above operation as the sample, the aluminum ion concentration, magnesium ion concentration, and calcium ion concentration were quantified in the same manner as in Measurement 1, and the results are summarized in Table 16. .
[測定5]樹脂組成物中的脂肪酸的量的測定 [Measurement 5] Measurement of the amount of fatty acid in the resin composition
使用實施例6、實施例9、實施例12及比較例8中所獲得的各樹脂組成物作為試樣,以與「測定2」相同的方法測定脂肪酸的量,並將結果彙總於表16中。 Using each resin composition obtained in Example 6, Example 9, Example 12 and Comparative Example 8 as a sample, the amount of fatty acid was measured by the same method as in "Measurement 2", and the results are summarized in Table 16. .
[測定6]樹脂組成物的氯仿可溶部分中的源自丙烯腈的成分的比例 [Measurement 6] The ratio of the acrylonitrile-derived component in the chloroform-soluble part of the resin composition
[1]乾燥試樣的製備 [1] Preparation of dry samples
使用實施例6、實施例9、實施例12及比較例8中所獲得的樹脂組成物,製備包含各樹脂組成物1質量%及氯仿99質量%的溶液,並進行以下(1)~(4)的操作而獲得「乾燥試樣」。 Using the resin compositions obtained in Example 6, Example 9, Example 12, and Comparative Example 8, a solution containing 1% by mass of each resin composition and 99% by mass of chloroform was prepared, and the following (1) to (4) ) To obtain a "dry sample".
(1)將所述溶液供於離心分離機並以20000rpm進行30分鐘離心分離。 (1) The solution was supplied to a centrifuge and centrifuged at 20000 rpm for 30 minutes.
(2)對上清液進行萃取,並放入至燒瓶內。 (2) Extract the supernatant and put it into the flask.
(3)將該燒瓶設置於溫度為68℃的恆溫槽中,並利用蒸發器自該上清液中餾去揮發成分。 (3) The flask was set in a constant temperature bath at a temperature of 68°C, and volatile components were distilled off from the supernatant with an evaporator.
(4)於溫度120℃下對該燒瓶內的殘存物進行3小時乾燥而獲得「乾燥試樣」。 (4) Dry the residue in the flask at a temperature of 120°C for 3 hours to obtain a "dry sample".
[2]氮含量的測定 [2] Determination of nitrogen content
進行所獲得的「乾燥試樣」(氯仿可溶部分)的元素分析,並測定氮含量Wn(質量%)。 The elemental analysis of the obtained "dry sample" (chloroform-soluble part) was performed, and the nitrogen content Wn (mass %) was measured.
[3]源自丙烯腈的成分的比例的算出 [3] Calculation of the ratio of acrylonitrile-derived components
藉由以下的算出式來算出源自丙烯腈的成分的比例Wacr(質量%)。 The ratio Wacr (mass %) of the component derived from acrylonitrile was calculated by the following calculation formula.
Wacr(質量%)=Wn(質量%)×53.06÷14.00‧‧‧(14) Wacr(mass%)=Wn(mass%)×53.06÷14.00‧‧‧(14)
丙烯腈的分子量:53.06 The molecular weight of acrylonitrile: 53.06
氮的分子量:14.00。 Molecular weight of nitrogen: 14.00.
[實施例1~實施例5及比較例1~比較例5] [Example 1 to Example 5 and Comparative Example 1 to Comparative Example 5]
1.樹脂組成物的製造 1. Manufacturing of resin composition
以表14中所示的組成調配製造例2中所獲得的含有橡膠的接枝共聚物(Csa-1)、調配有玻璃纖維的芳香族聚碳酸酯(「優必隆(Iupilon)GS2030M9001」(商品名),三菱工程塑膠(Mitsubishi Engineering-Plastics)(股份)製造,調配有30質量%(公稱)的玻璃纖維,芳香族聚碳酸酯樹脂的Mv:20000)、及芳香族聚碳酸 酯(商品名「優必隆(Iupilon)S3000」,三菱工程塑膠(股份)製造,Mv:20000),並進行混合,而獲得混合物。向將滾筒溫度加熱至310℃的脫揮式雙軸擠出機(池貝鐵工公司製造,PCM-30)中供給該混合物並進行混練,而製作調配有27質量%的玻璃纖維的實施例1的樹脂組成物的顆粒。 The rubber-containing graft copolymer (Csa-1) obtained in Manufacturing Example 2 and the aromatic polycarbonate ("Ubiron (Iupilon) GS2030M9001" ( Trade name), manufactured by Mitsubishi Engineering-Plastics (Stock), blended with 30% by mass (nominal) glass fiber, aromatic polycarbonate resin Mv: 20000), and aromatic polycarbonate Ester (trade name "Iupilon S3000", manufactured by Mitsubishi Engineering Plastics Co., Ltd., Mv: 20000), and mixed to obtain a mixture. The mixture was supplied and kneaded in a devolatilization twin-screw extruder (manufactured by Ikegai Iron Works, PCM-30) heated to a drum temperature of 310°C to produce Example 1 with 27% by mass of glass fiber The particles of the resin composition.
除將含有橡膠的接枝共聚物的種類及/或使用量、以及其他原料的調配量變更成表14中所示的條件以外,以與所述相同的方式製作實施例2~實施例5及比較例1~比較例5的各樹脂組成物的顆粒。再者,作為鹼金屬與強酸的鹽(D),於比較例3中,將十二基苯磺酸鈉(DBSNa)調配至樹脂組成物中,於比較例4中,將全氟丁磺酸鉀(F-114)調配至樹脂組成物中。 Except that the type and/or usage amount of the rubber-containing graft copolymer and the blending amount of other raw materials were changed to the conditions shown in Table 14, Example 2 to Example 5 were produced in the same manner as described above. The pellets of each resin composition of Comparative Example 1 to Comparative Example 5. Furthermore, as the salt (D) of an alkali metal and a strong acid, in Comparative Example 3, sodium dodecylbenzenesulfonate (DBSNa) was blended into the resin composition, and in Comparative Example 4, perfluorobutanesulfonic acid Potassium (F-114) is blended into the resin composition.
2.金屬及脂肪酸的含量的測定 2. Determination of metal and fatty acid content
根據「測定4」的方法,算出所獲得的各樹脂組成物100質量份中的鋁與強酸的鹽的含量(鋁換算量Wal)、鈣或鎂與強酸的鹽的含量(鈣換算量Wca及鎂換算量Wmg),並記載於表14中。 According to the method of "Measurement 4", calculate the content of the salt of aluminum and strong acid in 100 parts by mass of each resin composition obtained (aluminum conversion amount W al ), and the content of calcium or magnesium and the salt of a strong acid (calcium conversion amount W Ca and the magnesium conversion amount W mg ) are shown in Table 14.
於「測定2」的方法中,無法嚴格地區分脂肪酸的鹽(例如硬脂酸鈣)與不對鹽進行配位的脂肪酸(例如硬脂酸)。即,脂肪酸的測定值(Mdet莫耳)為樹脂組成物中所存在的脂肪酸的莫耳數Ma與脂肪酸鹽的莫耳數Ms的合計值,由下式表示。 In the method of "Assay 2", it is impossible to strictly distinguish between fatty acid salts (such as calcium stearate) and fatty acids that do not coordinate the salt (such as stearic acid). That is, the measured value of the fatty acid (Mdet mol) is the total value of the molar number Ma of the fatty acid present in the resin composition and the molar number Ms of the fatty acid salt, and is represented by the following formula.
Mdet=Ma+Ms‧‧‧(15) Mdet=Ma+Ms‧‧‧(15)
因此,於藉由「測定1」的方法而在含有橡膠的接枝聚合體中檢測出8ppm以上的鈣離子、鎂離子或鋁離子的金屬離子的情況,且藉由「測定2」的方法而檢測出脂肪酸的情況下,將該些金屬離子看作均源自脂肪酸鹽,並藉由下式來算出脂肪酸的莫耳數Ma。 Therefore, in the case where metal ions of calcium ion, magnesium ion or aluminum ion of 8 ppm or more are detected in the rubber-containing graft polymer by the method of "Measurement 1", and the method of "Measurement 2" When a fatty acid is detected, all these metal ions are considered to be derived from a fatty acid salt, and the molar number Ma of the fatty acid is calculated by the following formula.
Ma=Mdet-Ms‧‧‧(16) Ma=Mdet-Ms‧‧‧(16)
另外,於莫耳%的情況下,下式成立。 In addition, in the case of mole %, the following formula holds.
Ma(莫耳%)=Mdet(莫耳%)-Ms(莫耳%)‧‧‧(17)。 Ma(mole%)=Mdet(mole%)-Ms(mole%)‧‧‧(17).
藉由以下的計算例1及計算例2來說明根據脂肪酸的測定值(Mdet莫耳)算出實際存在的脂肪酸的量(Ma莫耳)的方法。 The following calculation example 1 and calculation example 2 illustrate the method of calculating the actual amount of fatty acid (Ma mol) based on the measured value of fatty acid (Mdet mol).
[計算例1] [Calculation example 1]
於檢測出1%的硬脂酸的情況,且檢測出100ppm(0.01%)的鋁、200ppm(0.02%)的鈣的情況下,各成分的莫耳%如下所示。 When 1% stearic acid is detected, and 100 ppm (0.01%) aluminum and 200 ppm (0.02%) calcium are detected, the molar% of each component is as follows.
硬脂酸的莫耳%:1%÷245(硬脂酸的分子量)=0.0040莫耳% Mole% of stearic acid: 1%÷245 (molecular weight of stearic acid)=0.0040 mole%
鋁的莫耳%:[0.01%÷27(鋁的分子量)]×3(價數)=0.0008莫耳% Mole% of aluminum: [0.01%÷27(molecular weight of aluminum)]×3(valence)=0.0008 mole%
鈣的莫耳%:[0.02%÷40(鈣的分子量)]×2(價數)=0.0010莫耳%。 Mole% of calcium: [0.02%÷40 (molecular weight of calcium)]×2(valence)=0.0010 mole%.
因此,脂肪酸的量Ma(莫耳%)藉由下式來算出。 Therefore, the amount of fatty acids Ma (mol%) is calculated by the following formula.
Ma(莫耳%)=Mdet(莫耳%)-Ms(莫耳%)=0.0040-0.0008-0.0010=0.0022 Ma(mole%)=Mdet(mole%)-Ms(mole%)=0.0040-0.0008-0.0010=0.0022
該脂肪酸的單位質量的濃度是藉由下式來算出。 The concentration per unit mass of the fatty acid is calculated by the following formula.
0.0022×245=0.54%。 0.0022×245=0.54%.
[計算例2] [Calculation example 2]
於檢測出0.5%的硬脂酸的情況,且檢測出100ppm(0.01%)的鋁、500ppm(0.05%)的鈣的情況下,各成分的莫耳%是藉由下式來算出。 When 0.5% stearic acid is detected, and 100 ppm (0.01%) aluminum and 500 ppm (0.05%) calcium are detected, the molar% of each component is calculated by the following formula.
硬脂酸的莫耳%:0.5%÷245(硬脂酸的分子量)=0.0020莫耳% Mole% of stearic acid: 0.5%÷245 (molecular weight of stearic acid)=0.0020 mole%
鋁的莫耳%:[0.01%÷27(鋁的分子量)]×3(價數)=0.0008莫耳% Mole% of aluminum: [0.01%÷27(molecular weight of aluminum)]×3(valence)=0.0008 mole%
鈣的莫耳%:[0.05%÷40(鈣的分子量)]×2(價數)=0.0025莫耳% Calcium mole%: [0.05%÷40(calcium molecular weight)]×2(valence)=0.0025 mole%
因此,脂肪酸的量Ma(莫耳%)是藉由下式來算出,且變成零以下。 Therefore, the amount of fatty acids Ma (mol%) is calculated by the following formula, and becomes below zero.
0.0020-0.0008-0.0025=-0.0013 0.0020-0.0008-0.0025=-0.0013
於此情況下,鋁均變成與硬脂酸的鹽,鈣的一部分變成與硬脂酸的鹽。剩餘的鈣變成與其他酸的鹽,其鈣濃度藉由下式來算 出。 In this case, all aluminum becomes a salt with stearic acid, and a part of calcium becomes a salt with stearic acid. The remaining calcium becomes a salt with other acids, and the calcium concentration is calculated by the following formula Out.
0.0013÷2×40=0.026(26ppm) 0.0013÷2×40=0.026(26ppm)
於製造含有橡膠的接枝聚合體時藉由乳化劑等來調配強酸與鹼金屬的鹽的情況下,將26ppm的鈣看作源自與強酸的鹽。 When a salt of a strong acid and an alkali metal is formulated with an emulsifier or the like when manufacturing a rubber-containing graft polymer, 26 ppm of calcium is regarded as the salt derived from the strong acid.
於所述計算例1中,當自脂肪酸的測定值(Mdet莫耳)減去對應於脂肪酸鹽的脂肪酸的值(Ms莫耳)時,參與形成與脂肪酸的鹽的金屬離子的分配順位為鋁、鎂、鈣的順序。其原因在於:鹼性高的順序為鋁、鎂、鈣的順序,且按鹼性自高至低的次序優先與脂肪酸形成鹽。 In the calculation example 1, when the value (Msmole) of the fatty acid corresponding to the fatty acid salt is subtracted from the measured value of the fatty acid (Mdetmole), the distribution order of the metal ion involved in the formation of the salt with the fatty acid is aluminum , Magnesium, calcium. The reason is that the order of high alkalinity is the order of aluminum, magnesium, and calcium, and the salt is formed with fatty acids first in order of alkalinity.
於使用聚合體(Csa-1)、聚合體(Csa-2)、聚合體(Csa-3)、聚合體(Cba-4)及聚合體(Cba-5)的實施例1~實施例5、比較例2及比較例4中,脂肪酸的含量少於0.03質量%,於聚合體中檢測出的鈣、鎂為與強酸的鹽。此處的強酸為十二基苯磺酸、烷基二苯基醚二磺酸等磺酸。 For the use of polymer (Csa-1), polymer (Csa-2), polymer (Csa-3), polymer (Cba-4) and polymer (Cba-5) in Examples 1 to 5, In Comparative Example 2 and Comparative Example 4, the fatty acid content was less than 0.03% by mass, and calcium and magnesium detected in the polymer were salts with strong acids. The strong acid here is sulfonic acid such as dodecylbenzenesulfonic acid and alkyl diphenyl ether disulfonic acid.
於使用聚合體(Cba-6)的比較例3中,鈣、鎂、及鋁的離子為檢測極限以下(少於8ppm),且包含1.4質量%的脂肪酸。於使用聚合體(Cba-7)的比較例5中,脂肪酸的含量少於0.03質量%,於聚合體中檢測出的鋁為與強酸的鹽。此處的強酸為十二基苯磺酸等磺酸。 In Comparative Example 3 using a polymer (Cba-6), the ions of calcium, magnesium, and aluminum were below the detection limit (less than 8 ppm) and contained 1.4% by mass of fatty acids. In Comparative Example 5 using the polymer (Cba-7), the fatty acid content was less than 0.03% by mass, and the aluminum detected in the polymer was a salt with a strong acid. The strong acid here is sulfonic acid such as dodecylbenzenesulfonic acid.
根據藉由「測定1」的方法及「測定2」的方法所測定的金屬量及脂肪酸的結果,算出各實施例及各比較例的相對於樹脂組成物的「主要三成分」100質量份的脂肪酸的量,且相對於芳 香族聚碳酸酯樹脂、玻璃填充劑及含有橡膠的接枝聚合體的合計100質量份,算出鋁、鈣或鎂與強酸的鹽的鋁換算量,以及鈣及鎂換算合計量,並記載於表14中。 Based on the results of the metal content and fatty acid measured by the method of "Measurement 1" and the method of "Measurement 2", calculate the amount of each example and each comparative example relative to 100 parts by mass of the "main three components" of the resin composition The amount of fatty acids, and relative to aromatic A total of 100 parts by mass of aromatic polycarbonate resin, glass filler, and rubber-containing graft polymer, calculate the aluminum conversion amount of aluminum, calcium or magnesium and the salt of strong acid, and the total calcium and magnesium conversion amount, and record it in Table 14.
3.查皮衝擊試驗 3. Charpy impact test
將所述10種的各顆粒分別個別地供給至住友射出成形機SE100DU(住友重機械工業(股份)製造)中,於氣缸溫度320℃、模具溫度90℃下,獲得長度80mm×寬度10mm×厚度4mm的成形體(試驗片)。查皮衝擊試驗是依據ISO-179-1,刻出依據ISO2818的A型的缺口來進行測定。將測定結果示於表14中。 Each of the 10 types of pellets were individually supplied to a Sumitomo injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries Co., Ltd.), and the cylinder temperature was 320°C and the mold temperature was 90°C to obtain a length of 80mm×width 10mm×thickness 4mm molded body (test piece). The chappel impact test is based on ISO-179-1, with a notch of Type A in accordance with ISO2818. The measurement results are shown in Table 14.
4.彎曲試驗 4. Bend test
將所述10種的各顆粒分別個別地供給至住友射出成形機SE100DU(住友重機械工業(股份)製造)中,於氣缸溫度320℃、模具溫度90℃下,獲得長度80mm×寬度10mm×厚度4mm的成形體(試驗片)。依據ISO-178,以2mm/min測定彎曲速度。將測定結果示於表14中。 Each of the 10 types of pellets were individually supplied to a Sumitomo injection molding machine SE100DU (manufactured by Sumitomo Heavy Industries Co., Ltd.), and the cylinder temperature was 320°C and the mold temperature was 90°C to obtain a length of 80mm×width 10mm×thickness 4mm molded body (test piece). According to ISO-178, the bending speed is measured at 2mm/min. The measurement results are shown in Table 14.
5.斷裂面的觀察 5. Observation of the fracture surface
實施於查皮衝擊試驗中斷裂的試驗片的斷裂面的掃描式電子顯微鏡(Scanning Electron Microscope,SEM)觀察,並評價芳香族聚碳酸酯樹脂與玻璃纖維的密接性。將各實施例、各比較例中所獲得的成形體的查皮衝擊試驗後的斷裂面彙總於圖1~圖7中。 The scanning electron microscope (Scanning Electron Microscope, SEM) observation of the fracture surface of the test piece fractured in the chappel impact test was performed, and the adhesiveness of an aromatic polycarbonate resin and glass fiber was evaluated. The fracture surfaces after the skin impact test of the molded body obtained in each example and each comparative example are summarized in FIGS. 1 to 7.
6.評價結果的彙總1 6. Summary of evaluation results 1
比較例1為玻璃纖維(玻璃填充劑)27%的芳香族聚碳酸酯樹脂組成物。比較例2為將樹脂組成物中的玻璃纖維的含量固定為27%,並調配有含有橡膠的接枝聚合體(Csa-2)的例子。相對於芳香族聚碳酸酯樹脂及含有橡膠的接枝聚合體的合計(樹脂組 成物的「主要三成分」)100份,源自含有橡膠的接枝聚合體(C)的鈣或鎂與強酸的鹽以鈣及鎂換算計為0.0185份,而超過0.0008份。因此,使玻璃纖維與芳香族聚碳酸酯樹脂的密接性下降(圖5)。因密接性下降,故無缺口而查皮衝擊強度未得到改善,反而下降。進而,由調配玻璃纖維所產生的彎曲特性改善效果亦顯著降低。 Comparative Example 1 is an aromatic polycarbonate resin composition of 27% glass fiber (glass filler). Comparative Example 2 is an example in which the content of glass fibers in the resin composition is fixed to 27%, and a graft polymer (Csa-2) containing rubber is prepared. Compared to the total of aromatic polycarbonate resin and rubber-containing graft polymer (resin group The "main three components") 100 parts of the finished product, derived from the rubber-containing graft polymer (C) of calcium or magnesium and a salt of a strong acid, are 0.0185 parts in terms of calcium and magnesium, which exceeds 0.0008 parts. Therefore, the adhesion between the glass fiber and the aromatic polycarbonate resin is reduced (Figure 5). Due to the decrease in adhesion, there is no gap and the peel impact strength is not improved, but decreased. Furthermore, the effect of improving the bending characteristics of the glass fiber is also significantly reduced.
比較例3為調配有含有橡膠的接枝聚合體(Cba-6)的例子。含有橡膠的接枝聚合體(Cba-6)包含1.4%的脂肪酸。因此,玻璃纖維與芳香族聚碳酸酯樹脂的密接性下降(圖6)。因密接性下降,故查皮衝擊強度未得到改善,反而下降。進而,由調配玻璃纖維所產生的彎曲特性改善效果亦顯著降低。比較例4中,相對於樹脂組成物的「主要三成分」100份,源自含有橡膠的接枝聚合體(C)的鈣及/或鎂與強酸的鹽的合計含量以鈣及鎂換算的合計含量計為0.0028份,而超過0.0008份。因此,使玻璃纖維與芳香族聚碳酸酯樹脂的密接性下降(圖2)。無缺口查皮衝擊強度未得到改善,進而,由調配玻璃纖維所產生的彎曲特性改善效果亦顯著降低。 Comparative Example 3 is an example of blending a graft polymer (Cba-6) containing rubber. The rubber-containing graft polymer (Cba-6) contains 1.4% fatty acids. Therefore, the adhesiveness of the glass fiber and the aromatic polycarbonate resin is decreased (Figure 6). Due to the decrease in adhesion, the impact strength of the skin has not been improved, but has decreased. Furthermore, the effect of improving the bending characteristics of the glass fiber is also significantly reduced. In Comparative Example 4, the total content of calcium and/or magnesium and strong acid salt derived from the graft polymer (C) containing rubber is calculated in terms of calcium and magnesium relative to 100 parts of the "main three components" of the resin composition The total content is 0.0028 parts and exceeds 0.0008 parts. Therefore, the adhesion between the glass fiber and the aromatic polycarbonate resin is reduced (Figure 2). The unnotched peel impact strength has not been improved, and furthermore, the effect of improving the bending characteristics of the glass fiber is also significantly reduced.
比較例5為調配有含有橡膠的接枝聚合體(Cba-7)的例子。當於樹脂組成物中調配有10%的含有橡膠的接枝聚合體(Cba-7)時,相對於樹脂組成物的「主要三成分」100份,源自含有橡膠的接枝聚合體(C)的鋁與強酸的鹽的含量以鋁換算量計為0.0014份,而超過0.0008份。因此,玻璃纖維與芳香族聚碳酸 酯樹脂的密接性下降(圖7)。因密接性下降,故查皮衝擊強度未得到改善,反而下降。進而,由調配玻璃纖維所產生的彎曲特性改善效果亦顯著降低。 Comparative Example 5 is an example of blending a graft polymer (Cba-7) containing rubber. When 10% rubber-containing graft polymer (Cba-7) is blended in the resin composition, relative to 100 parts of the "main three components" of the resin composition, it is derived from the rubber-containing graft polymer (Cba-7). The content of the salt of aluminum and strong acid of) is 0.0014 parts in terms of aluminum conversion amount, and exceeds 0.0008 parts. Therefore, glass fiber and aromatic polycarbonate The adhesiveness of the ester resin is reduced (Figure 7). Due to the decrease in adhesion, the impact strength of the skin has not been improved, but has decreased. Furthermore, the effect of improving the bending characteristics of the glass fiber is also significantly reduced.
實施例1~實施例5中,所使用的含有橡膠的接枝聚合體(C)的丙酮不溶部分為25質量%以上,含有橡膠的接枝聚合體(C)中所含的脂肪酸的量為1質量%以下,相對於樹脂組成物的「主要三成分」100質量份,源自含有橡膠的接枝聚合體(C)的鈣或鎂與強酸的鹽的合計含量以鈣及鎂換算的合計含量計為0.0008份以下,鋁與強酸的鹽的含量以鋁換算的含量計為0.0008份以下。有缺口及無缺口均使成形體的衝擊強度得到改良。與不含含有橡膠的接枝聚合體的樹脂組成物(比較例1)相比,包含10質量份的含有橡膠的接枝聚合體的樹脂組成物(實施例3)的成形體的彎曲強度下降。包含2.5質量份~5質量份的含有橡膠的接枝聚合體的樹脂組成物(實施例1、實施例2、實施例4、實施例5)的成形體的彎曲強度為與不含含有橡膠的接枝聚合體的樹脂組成物的成形體的彎曲強度(比較例1)相同的程度,且有缺口及無缺口均使成形體的衝擊強度得到改良。實施例3與比較例2、比較例4、比較例5的含有橡膠的接枝聚合體的聚合物的構成成分大致相同,且含有橡膠的接枝聚合體的調配量亦相同,但源自含有橡膠的接枝聚合體(C)的鈣及鎂與強酸的鹽的合計含量的鈣及鎂換算的合計含量、或鋁與強酸的鹽的含量的鋁換算的含量不同。樹脂組成物中的源自含有橡膠的接枝聚合體(C)的鈣及鎂與強酸 的鹽的合計含量的鈣及鎂換算的合計含量、或鋁與強酸的鹽的含量的鋁換算的含量越多,成形體的彎曲強度或查皮衝擊強度等機械強度越低。根據圖1與圖2、圖5、圖7,可知與比較例2、比較例4或比較例5的包含含有橡膠的接枝聚合體的樹脂組成物相比,實施例3的包含含有橡膠的接枝聚合體的樹脂組成物的玻璃纖維與芳香族聚碳酸酯的密接性更優異。 In Examples 1 to 5, the acetone-insoluble portion of the rubber-containing graft polymer (C) used was 25% by mass or more, and the amount of fatty acid contained in the rubber-containing graft polymer (C) was 1% by mass or less, relative to 100 parts by mass of the "main three components" of the resin composition, the total content of the salt of calcium or magnesium derived from the rubber-containing graft polymer (C) and strong acid is calculated as the total of calcium and magnesium The content is 0.0008 parts or less, and the content of the salt of aluminum and strong acid is 0.0008 parts or less in terms of aluminum conversion content. Both notched and unnotched improved the impact strength of the formed body. Compared with the resin composition containing no graft polymer containing rubber (Comparative Example 1), the flexural strength of the molded body of the resin composition containing 10 parts by mass of the graft polymer containing rubber (Example 3) decreased . The flexural strength of the molded body of the resin composition (Example 1, Example 2, Example 4, and Example 5) containing 2.5 parts by mass to 5 parts by mass of the graft polymer containing rubber The flexural strength of the molded body of the resin composition of the graft polymer (Comparative Example 1) is about the same, and the impact strength of the molded body is improved both with and without notches. Example 3 and Comparative Example 2, Comparative Example 4, and Comparative Example 5 have almost the same constituents of the rubber-containing graft polymer polymer, and the blending amount of the rubber-containing graft polymer is also the same. The rubber graft polymer (C) differs from the total content of calcium and magnesium in terms of the total content of calcium and magnesium and the salt of strong acid, or the content of aluminum and the salt of strong acid in terms of aluminum. Calcium and magnesium derived from graft polymer (C) containing rubber and strong acid in resin composition The greater the total content of the salt in terms of the total content of calcium and magnesium, or the content of the salt of aluminum and strong acid, the lower the mechanical strength such as the bending strength and the skin impact strength of the molded body. According to Fig. 1 and Fig. 2, Fig. 5 and Fig. 7, it can be seen that the rubber-containing graft polymer-containing resin composition of Example 3 is compared with the resin composition of Comparative Example 2, Comparative Example 4 or Comparative Example 5. The adhesion between the glass fiber of the resin composition of the graft polymer and the aromatic polycarbonate is more excellent.
[實施例6~實施例14及比較例6~比較例8] [Example 6 to Example 14 and Comparative Example 6 to Comparative Example 8]
1.樹脂組成物的製造 1. Manufacturing of resin composition
以表15中所示的組成調配製造例2中所獲得的含有橡膠的接枝共聚物(Csa-1)、調配有玻璃纖維的芳香族聚碳酸酯(「優必隆(Iupilon)GS2030M9001」(商品名),三菱工程塑膠(股份)製造,調配有30質量%(公稱)的玻璃纖維,芳香族聚碳酸酯樹脂的Mv:20000)、及芳香族聚碳酸酯(商品名「優必隆(Iupilon)S3000」,三菱工程塑膠(股份)製造,Mv:20000),並進行混合。向將滾筒溫度加熱至280℃的脫揮式雙軸擠出機(池貝鐵工公司製造,PCM-30)中供給該混合物並進行混練,而製作調配有27質量%的玻璃纖維的實施例6的樹脂組成物的顆粒。 The rubber-containing graft copolymer (Csa-1) obtained in Manufacturing Example 2 and the aromatic polycarbonate ("Ubiron (Iupilon) GS2030M9001" ( Product name), manufactured by Mitsubishi Engineering Plastics (Stock), blended with 30% by mass (nominal) of glass fiber, aromatic polycarbonate resin Mv: 20000), and aromatic polycarbonate (trade name "Ubiron ( Iupilon) S3000", manufactured by Mitsubishi Engineering Plastics Co., Ltd., Mv: 20000), and mixed. The mixture was supplied and kneaded in a devolatilization twin-screw extruder (manufactured by Ikegai Iron Works, PCM-30) heated to a drum temperature of 280°C to produce Example 6 with 27% by mass of glass fiber The particles of the resin composition.
除將含有橡膠的接枝共聚物(C)的種類及/或使用量、以及其他原料的調配量變更成表15中所示的條件以外,以與所述相同的方式製作實施例7~實施例18及比較例6~比較例8的各樹脂組成物的顆粒。再者,於實施例8、實施例11及比較例7中,將二苯基碸磺酸鉀(KSS)調配至樹脂組成物中,於實施例10中, 將全氟丁磺酸鉀(F-114)調配至樹脂組成物中。 Except that the type and/or usage amount of the rubber-containing graft copolymer (C) and the blending amount of other raw materials were changed to the conditions shown in Table 15, Example 7 to implementation were made in the same manner as described above The pellets of each resin composition of Example 18 and Comparative Example 6 to Comparative Example 8. Furthermore, in Example 8, Example 11 and Comparative Example 7, potassium diphenylsulfonate (KSS) was blended into the resin composition. In Example 10, Potassium perfluorobutanesulfonate (F-114) is blended into the resin composition.
2.金屬及脂肪酸的含量的測定 2. Determination of metal and fatty acid content
根據藉由「測定1」的方法及「測定2」的方法所測定的金屬量及脂肪酸的結果,算出各實施例及各比較例的相對於樹脂組成物的「主要三成分」100質量份的脂肪酸的量,且相對於芳香族聚碳酸酯樹脂、玻璃填充劑及含有橡膠的接枝聚合體的合計100質量份,算出鋁、鈣及鎂與強酸的鹽的鈣及鎂換算量,並記載於表15中。 Based on the results of the metal content and fatty acid measured by the method of "Measurement 1" and the method of "Measurement 2", calculate the amount of each example and each comparative example relative to 100 parts by mass of the "main three components" of the resin composition The amount of fatty acid is calculated based on the total amount of 100 parts by mass of the aromatic polycarbonate resin, glass filler, and rubber-containing graft polymer, and the calcium and magnesium conversion amounts of the salt of aluminum, calcium, and magnesium with strong acids are recorded and described In Table 15.
於含有橡膠的接枝聚合體(Csa-1)、含有橡膠的接枝聚合體(Csa-3)及含有橡膠的接枝聚合體(Csa-8)中不含脂肪酸或其鹽,因此於該些聚合體中檢測出的鈣及鎂為與強酸的鹽。 The rubber-containing graft polymer (Csa-1), rubber-containing graft polymer (Csa-3), and rubber-containing graft polymer (Csa-8) do not contain fatty acids or their salts. The calcium and magnesium detected in these polymers are salts with strong acids.
於實施例12~實施例14中,調配有硬脂酸鈣或硬脂酸鎂。算出其加入值,且相對於樹脂組成物的「主要三成分」100質量份,分別算出鈣及鎂與弱酸的鹽的鈣及鎂換算量。 In Example 12 to Example 14, calcium stearate or magnesium stearate was prepared. The added value was calculated, and the calcium and magnesium conversion amounts of the salt of calcium and magnesium and the weak acid were calculated with respect to 100 parts by mass of the "main three components" of the resin composition.
3.查皮衝擊試驗 3. Charpy impact test
除將氣缸溫度變更成280℃以外,與實施例1同樣地進行查皮衝擊試驗。將測定結果示於表15中。 Except for changing the cylinder temperature to 280°C, the skin-checking impact test was performed in the same manner as in Example 1. The measurement results are shown in Table 15.
4.彎曲試驗 4. Bend test
除將氣缸溫度變更成280℃以外,與實施例1同樣地進行彎曲試驗。將測定結果示於表15中。 Except for changing the cylinder temperature to 280°C, a bending test was performed in the same manner as in Example 1. The measurement results are shown in Table 15.
5.評價結果的彙總2 5. Summary of evaluation results 2
若彙總以上的評價結果,則如下所示。 The above evaluation results are summarized as follows.
實施例6~實施例14及比較例6~比較例8為將擠出溫度、成形溫度設為280℃所獲得的樹脂組成物的評價結果。比較例8為玻璃纖維27質量%的芳香族聚碳酸酯樹脂組成物。比較例6、比較例7中,相對於樹脂組成物的「主要三成分」100質量份,源自含有橡膠的接枝聚合體(C)的鈣及鎂與強酸的鹽的合計含量超過0.0008質量份,成形體的衝擊強度並不充分,彎曲強度的下降特別大。 Examples 6 to 14 and Comparative Examples 6 to 8 are evaluation results of resin compositions obtained by setting the extrusion temperature and the molding temperature to 280°C. Comparative Example 8 is an aromatic polycarbonate resin composition containing 27% by mass of glass fibers. In Comparative Example 6 and Comparative Example 7, the total content of the salt of calcium and magnesium derived from the rubber-containing graft polymer (C) and strong acid with respect to 100 parts by mass of the "main three components" of the resin composition exceeded 0.0008 mass However, the impact strength of the molded body is not sufficient, and the reduction in bending strength is particularly large.
實施例6~實施例14中,相對於樹脂組成物的「主要三成分」100質量份,源自含有橡膠的接枝聚合體(C)的鈣及鎂與強酸的鹽的合計含量以鈣及鎂換算的合計含量計為0.0008質量份以下,成形體的衝擊強度優異。 In Examples 6 to 14, relative to 100 parts by mass of the "main three components" of the resin composition, the total content of calcium and magnesium derived from the rubber-containing graft polymer (C) and the salt of a strong acid is calcium and The total content in terms of magnesium is 0.0008 parts by mass or less, and the impact strength of the molded body is excellent.
根據實施例7與實施例8的比較、以及實施例9與實施例10及實施例11的比較,藉由調配二苯基碸磺酸鉀(KSS)等鹼金屬與強酸的鹽(D),而確認到成形體的彎曲強度的改善。於實施例11中,亦看到衝擊強度的改良。 According to the comparison between Example 7 and Example 8, and the comparison between Example 9 and Example 10 and Example 11, by formulating alkali metal and strong acid salts (D) such as potassium diphenylsulfonate (KSS), The improvement of the bending strength of the molded body was confirmed. In Example 11, an improvement in impact strength was also seen.
實施例12~實施例14為於擠出時將鈣或鎂與弱酸的鹽調配至實施例6的樹脂組成物中者。即便樹脂組成物的「主要三成分」100質量份中的鈣或鎂與酸的鹽的合計含量以鈣及鎂換算的合計含量計為0.0008質量份以上,與實施例6相比,成形體的衝擊強度及/或彎曲特性亦得到改善。根據實施例12~實施例14,可知若樹脂組成物的「主要三成分」100質量份中的鈣或鎂與弱酸的鹽的合計含量以鈣及鎂換算的合計含量計為0.0010~0.0060的範 圍,則成形體的彎曲特性或無缺口查皮衝擊強度特別優異。 Examples 12 to 14 are those in which a salt of calcium or magnesium and a weak acid is blended into the resin composition of Example 6 during extrusion. Even if the total content of calcium or magnesium and acid salt in 100 parts by mass of the "main three components" of the resin composition is 0.0008 parts by mass or more in terms of calcium and magnesium, compared with Example 6, the molded body has Impact strength and/or bending characteristics are also improved. According to Examples 12 to 14, it can be seen that if the total content of calcium or magnesium and the salt of weak acid in 100 parts by mass of the "main three components" of the resin composition is in the range of 0.0010 to 0.0060 as the total content of calcium and magnesium conversion The bending properties of the formed body and the unnotched skin impact strength are particularly excellent.
6.利用測定4~測定6進行的評價 6. Evaluation by measurement 4 to measurement 6
針對實施例6、實施例9、實施例12及比較例8的各樹脂組成物,根據所述測定4、測定5及測定6來測定各成分的量,並將評價結果彙總於表16中。 For each resin composition of Example 6, Example 9, Example 12, and Comparative Example 8, the amount of each component was measured in accordance with the aforementioned Measurement 4, Measurement 5, and Measurement 6, and the evaluation results are summarized in Table 16.
實施例6、實施例9、實施例12的各樹脂組成物滿足本發明的第一形態的樹脂組成物的所有必要條件,所獲得的樹脂組成物的成形體的衝擊強度優異。 Each resin composition of Example 6, Example 9, and Example 12 satisfies all the requirements of the resin composition of the first aspect of the present invention, and the obtained molded body of the resin composition has excellent impact strength.
藉由測定樹脂組成物中的氯仿可溶部分的鈣、鎂及鋁的 含量,大致可測定樹脂組成物中所含的源自與強酸的鹽的鈣、鎂的含量及源自與強酸的鹽的鋁的含量。 By measuring the chloroform-soluble part of calcium, magnesium and aluminum in the resin composition The content can roughly measure the content of calcium and magnesium derived from the salt with a strong acid and the content of aluminum derived from the salt with the strong acid contained in the resin composition.
玻璃填充劑(B)難以溶解於氯仿中,因此於樹脂組成物中的氯仿可溶部分中,幾乎不含玻璃填充劑(B)中所含的金屬成分。於實施例及比較例中,在調配至樹脂組成物中的玻璃纖維中包含4質量%左右的鈣、0.2質量%左右的鎂、2質量%左右的鋁。比較例8的「測定方法X」後所獲得的樹脂組成物中的鈣、鎂及鋁為檢測極限(2ppm)以下。可判斷於「測定方法X」後的樹脂組成物(乾燥試樣)100質量份中不含0.0002質量份以上的源自玻璃纖維的鈣、鎂及鋁,因此於對上清液進行萃取時未實施使用過濾器的過濾。 The glass filler (B) is difficult to dissolve in chloroform, so the chloroform-soluble part in the resin composition hardly contains the metal component contained in the glass filler (B). In the examples and comparative examples, the glass fiber blended into the resin composition contains about 4% by mass of calcium, about 0.2% by mass of magnesium, and about 2% by mass of aluminum. The calcium, magnesium, and aluminum in the resin composition obtained after the "Measuring Method X" of Comparative Example 8 were below the detection limit (2 ppm). It can be judged that 100 parts by mass of the resin composition (dry sample) after "Measuring Method X" does not contain 0.0002 parts by mass or more of calcium, magnesium, and aluminum derived from glass fibers. Therefore, the supernatant was not extracted. Implement filtering using filters.
藉由測定樹脂組成物中的氯仿可溶部分的鈣、鎂及鋁量,可大致將鈣或鎂與強酸的鹽的合計含量作為鈣及鎂換算的合計含量而求出,另外,將鋁與強酸的鹽的含量作為鋁換算的含量而求出。其原因在於:鈣或鎂與弱酸的鹽、特別是鈣或鎂與脂肪酸的鹽難以溶解於氯仿中。 By measuring the amount of calcium, magnesium, and aluminum in the chloroform-soluble part of the resin composition, the total content of calcium or magnesium and the salt of a strong acid can be roughly calculated as the total content of calcium and magnesium conversion. The content of the salt of the strong acid is calculated as the content in terms of aluminum. The reason is that the salt of calcium or magnesium and a weak acid, especially the salt of calcium or magnesium and a fatty acid, is difficult to dissolve in chloroform.
再者,於實施例12的樹脂組成物中,相對於芳香族聚碳酸酯樹脂及含有橡膠的接枝聚合體的合計(樹脂二成分)100質量份,以鈣換算的含量計調配有0.0020÷(1-0.27)=0.0027質量份(27ppm)的作為鈣與弱酸的鹽的硬脂酸鈣。但是,於「測定4」的「樹脂組成物中的鋁離子量、鎂離子量、鈣離子量的定量」的結果中,鈣的量變成檢測極限以下(2ppm以下:相對於樹脂二成 分100質量份為0.0002質量份以下)。其表示藉由測定方法X而去除了作為鈣與弱酸的鹽的硬脂酸鈣。 In addition, in the resin composition of Example 12, with respect to 100 parts by mass of the total (resin two components) of the aromatic polycarbonate resin and the rubber-containing graft polymer, the content in terms of calcium is adjusted to 0.0020÷ (1-0.27)=0.0027 parts by mass (27 ppm) of calcium stearate which is a salt of calcium and a weak acid. However, in the result of "Quantification of the amount of aluminum ion, magnesium ion, and calcium ion in the resin composition" in "Measurement 4", the amount of calcium fell below the detection limit (2 ppm or less: 20% relative to the resin 100 parts by mass is 0.0002 parts by mass or less). It means that calcium stearate, which is a salt of calcium and a weak acid, was removed by the measurement method X.
[產業上之可利用性] [Industrial availability]
藉由本發明所獲得的樹脂組成物使先前於芳香族聚碳酸酯系基質中困難的玻璃填充劑的密接性的提昇與橡膠分散性的改良併存,其成形體具有優異的衝擊特性與剛性。因此,可應用於包含要求薄壁化與尺寸穩定性的汽車構件或家電構件等的各種領域的原材料。 The resin composition obtained by the present invention coexists the improvement of the adhesion of the glass filler and the improvement of the rubber dispersibility, which were previously difficult in the aromatic polycarbonate matrix, and the molded body has excellent impact characteristics and rigidity. Therefore, it can be applied to materials in various fields including automotive components and home appliances components that require thinning and dimensional stability.
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