WO2019146782A1 - アクリル系重合体凝固物 - Google Patents
アクリル系重合体凝固物 Download PDFInfo
- Publication number
- WO2019146782A1 WO2019146782A1 PCT/JP2019/002731 JP2019002731W WO2019146782A1 WO 2019146782 A1 WO2019146782 A1 WO 2019146782A1 JP 2019002731 W JP2019002731 W JP 2019002731W WO 2019146782 A1 WO2019146782 A1 WO 2019146782A1
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- WIPO (PCT)
- Prior art keywords
- mass
- polymer
- coagulated
- acetone
- acrylic polymer
- Prior art date
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- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 84
- 239000002245 particle Substances 0.000 claims abstract description 47
- 230000009477 glass transition Effects 0.000 claims abstract description 26
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 23
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 180
- 229920000642 polymer Polymers 0.000 claims description 138
- 239000004816 latex Substances 0.000 claims description 51
- 229920000126 latex Polymers 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 44
- 239000000463 material Substances 0.000 claims description 40
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 37
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 37
- 239000000126 substance Substances 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 30
- 238000005345 coagulation Methods 0.000 claims description 25
- 230000015271 coagulation Effects 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 24
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 239000003431 cross linking reagent Substances 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000000701 coagulant Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 229920001169 thermoplastic Polymers 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 230000001112 coagulating effect Effects 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 238000005185 salting out Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 88
- 238000006116 polymerization reaction Methods 0.000 description 43
- 230000002087 whitening effect Effects 0.000 description 40
- 229920001971 elastomer Polymers 0.000 description 36
- 239000011347 resin Substances 0.000 description 32
- 229920005989 resin Polymers 0.000 description 32
- 239000000047 product Substances 0.000 description 30
- 239000004925 Acrylic resin Substances 0.000 description 29
- 229920000178 Acrylic resin Polymers 0.000 description 29
- 239000010410 layer Substances 0.000 description 27
- 239000002002 slurry Substances 0.000 description 27
- -1 defoamers Substances 0.000 description 21
- 239000002253 acid Substances 0.000 description 18
- 238000009835 boiling Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000007423 decrease Effects 0.000 description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 238000004220 aggregation Methods 0.000 description 12
- 230000002776 aggregation Effects 0.000 description 12
- 239000011258 core-shell material Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 238000005469 granulation Methods 0.000 description 11
- 230000003179 granulation Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 208000005156 Dehydration Diseases 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 239000000839 emulsion Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000004926 polymethyl methacrylate Substances 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000012615 aggregate Substances 0.000 description 6
- 238000000149 argon plasma sintering Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000012792 core layer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000006096 absorbing agent Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 4
- 230000016615 flocculation Effects 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 235000019341 magnesium sulphate Nutrition 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 238000005453 pelletization Methods 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- 241001093575 Alma Species 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 2
- VCYCUECVHJJFIQ-UHFFFAOYSA-N 2-[3-(benzotriazol-2-yl)-4-hydroxyphenyl]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 VCYCUECVHJJFIQ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- RNOOHTVUSNIPCJ-UHFFFAOYSA-N butan-2-yl prop-2-enoate Chemical compound CCC(C)OC(=O)C=C RNOOHTVUSNIPCJ-UHFFFAOYSA-N 0.000 description 2
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 2
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 2
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- JHCAASGQBQNAKN-UHFFFAOYSA-N 1-bicyclo[2.2.1]hept-2-enyl prop-2-enoate Chemical compound C(C=C)(=O)OC12C=CC(CC1)C2 JHCAASGQBQNAKN-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- DABFKTHTXOELJF-UHFFFAOYSA-N 1-propylpyrrole-2,5-dione Chemical compound CCCN1C(=O)C=CC1=O DABFKTHTXOELJF-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 description 1
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- FVCPXLWAKNJIKK-UHFFFAOYSA-N Dimexano Chemical compound COC(=S)SSC(=S)OC FVCPXLWAKNJIKK-UHFFFAOYSA-N 0.000 description 1
- FVIGODVHAVLZOO-UHFFFAOYSA-N Dixanthogen Chemical compound CCOC(=S)SSC(=S)OCC FVIGODVHAVLZOO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- PCVSIMQAFWRUEC-UHFFFAOYSA-N N2-[1-[methyl-(phenylmethyl)amino]-3-(2-naphthalenyl)-1-oxopropan-2-yl]-N1-(2-nitrophenyl)pyrrolidine-1,2-dicarboxamide Chemical compound C=1C=C2C=CC=CC2=CC=1CC(NC(=O)C1N(CCC1)C(=O)NC=1C(=CC=CC=1)[N+]([O-])=O)C(=O)N(C)CC1=CC=CC=C1 PCVSIMQAFWRUEC-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- OXOPJTLVRHRSDJ-SNAWJCMRSA-N [(e)-but-2-enyl] 2-methylprop-2-enoate Chemical compound C\C=C\COC(=O)C(C)=C OXOPJTLVRHRSDJ-SNAWJCMRSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 229910001963 alkali metal nitrate Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- 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 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- LCPUDZUWZDSKMX-UHFFFAOYSA-K azane;hydrogen sulfate;iron(3+);sulfate;dodecahydrate Chemical compound [NH4+].O.O.O.O.O.O.O.O.O.O.O.O.[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LCPUDZUWZDSKMX-UHFFFAOYSA-K 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- DPEYVZPMZDHWIG-UHFFFAOYSA-L disodium;nonoxybenzene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.CCCCCCCCCOC1=CC=CC=C1 DPEYVZPMZDHWIG-UHFFFAOYSA-L 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 229960002377 dixanthogen Drugs 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- ZWEDFBKLJILTMC-UHFFFAOYSA-N ethyl 4,4,4-trifluoro-3-hydroxybutanoate Chemical compound CCOC(=O)CC(O)C(F)(F)F ZWEDFBKLJILTMC-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- GOZDOXXUTWHSKU-UHFFFAOYSA-N pentadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCOC(=O)C=C GOZDOXXUTWHSKU-UHFFFAOYSA-N 0.000 description 1
- ULDDEWDFUNBUCM-UHFFFAOYSA-N pentyl prop-2-enoate Chemical compound CCCCCOC(=O)C=C ULDDEWDFUNBUCM-UHFFFAOYSA-N 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/14—Treatment of polymer emulsions
- C08F6/22—Coagulation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
- C08L33/12—Homopolymers or copolymers of methyl methacrylate
Definitions
- the present invention relates to an acrylic polymer coagulated material and a method for producing the same. More particularly, the present invention relates to a coagulum which is excellent in transparency, hot water whitening resistance, stress whitening resistance, film forming property, and heat shrinkage resistance. The present invention also relates to a molded article, a film and a laminate obtained by using an acrylic polymer coagulated product.
- Acrylic resins have excellent weatherability, design and transparency, but on the other hand have the drawback of being inferior in impact resistance and toughness, and based on the core-shell structure as an improvement of the disadvantages,
- Various acrylic multilayer structural polymers in which a soft layer and a hard layer are combined have been studied.
- An acrylic multilayer structure polymer is generally used after coagulating a polymer latex produced by emulsion polymerization, followed by dehydration and drying, being recovered as a powdery coagulated substance and being formed into a sheet or a film.
- water-soluble substances such as initiators, emulsifiers, defoamers, coagulants, etc. remain in the coagulated substance, whitening occurs when the molded article is immersed in warm water or continuously used in a high temperature and high humidity environment. Had a problem (hereinafter referred to as hot water whitening).
- Patent document 1 is made of an acrylic resin in which rubber particles are dispersed in a methacrylic resin, and the content of a water-soluble substance is 200 ppm or less, and it is 1 hour in warm water of 80 ° C. It discloses an acrylic resin film having a haze value of 5% or less after immersion and a thickness of 50 ⁇ m or more and 600 ⁇ m or less.
- An object of the present invention is to provide an acrylic polymer coagulated material which is excellent in transparency, weather resistance, hot water whitening resistance and white water resistance.
- a multilayer acrylic polymer aggregate having a bulk density of 0.3 to 0.6 g / cm 3 , a median diameter of 50 to 400 ⁇ m, and a ratio of particles having a particle size of 75 ⁇ m or less of 50% or less, And the alkali metal and alkaline earth metal to contain satisfy
- N amount of alkali metal and alkaline earth metal contained in the coagulated substance (mmoL / kg), Tg; glass transition temperature of acetone solubles (° C.) a; valence of alkali metal and alkaline earth metal contained in the coagulated substance.
- the multilayer acrylic polymer is acetone soluble and insoluble in acetone, acetone soluble is 80 to 99% by mass of structural unit derived from methyl methacrylate, and carbon number of alkyl group is 1 to 8 Structural unit derived from a certain alkyl acrylate, containing 1 to 20% by mass, having a glass transition temperature of 80 to 100 ° C, acetone insoluble content 20 to 60% by mass derived from methyl methacrylate, carbon number of alkyl group A coagulated material according to [1] or [2], comprising 40 to 80% by mass of a structural unit derived from an alkyl acrylate having 1 to 8 and having a glass transition temperature of 0 ° C. or less.
- the multilayer acrylic polymer is composed of an acetone soluble component and an acetone insoluble component, and the acetone soluble component is 80 to 99% by mass of a structural unit derived from methyl methacrylate, and an alkyl group having 1 to 8 carbon atoms Structural unit derived from an alkyl acrylate having 1 to 20% by mass, having a glass transition temperature of 90 to 110 ° C., and having an acetone insoluble component derived from methyl methacrylate 40 to 60% by mass, carbon number of alkyl group Containing 40 to 60% by mass of a structural unit derived from an alkyl acrylate having 1 to 8 and 0 to 20% by mass of a vinyl monomer copolymerizable therewith, and having a glass transition temperature of 0 ° C. or less [1] Or the coagulated material according to [2].
- [5] A formed body obtained by using the coagulated material according to any one of [1] to [4].
- [6] A film obtained by using the coagulated material according to any one of [1] to [4].
- a laminate comprising at least one layer comprising a film obtained using the coagulated material according to any one of [7] [1] to [4] and at least one layer comprising another thermoplastic polymer molded article body.
- Step 1 A step of polymerizing an acrylic monomer, another copolymerizable monomer, a grafting agent and / or a crosslinking agent in the presence of an emulsifier to obtain a latex (I)
- Step 2 A step of polymerizing an acrylic monomer, another copolymerizable other monomer, a grafting agent and an optional crosslinking agent in the presence of the latex (I) to obtain a latex (II)
- Step 3 Step of polymerizing an acrylic monomer in the presence of latex (II) to obtain latex (III)
- Step 4 Loosely coagulating the latex (III) in the presence of a coagulant to obtain an aggregate of a multilayer acrylic polymer
- Step 5 The aggregate of the multilayer acrylic polymer obtained in Step 4 is heated to obtain a coagulated multilayer polymer, and the bulk density is 0.3 to 0.6 g / cm.
- a multilayer acrylic resin characterized in that the ratio of particles having a median diameter of 50 to 400 ⁇ m and a particle diameter of 75 ⁇ m or less is 50% or less, and the contained alkali metal and alkaline earth metal satisfy the following formula (1) Method of producing a polymer coagulated material.
- N amount of alkali metal and alkaline earth metal contained in the coagulated substance (mmoL / kg), Tg; glass transition temperature of acetone solubles (° C.) a; valence of alkali metal and alkaline earth metal contained in the coagulated substance.
- the acrylic monomer preferably contains methyl methacrylate and alkyl acrylate.
- the acrylic polymer coagulated material of the present invention and a molded product, a film and a laminate obtained using the same are excellent in transparency, weather resistance, hot water whitening resistance and boiling water whitening resistance.
- the coagulated substance of the present invention contains a multilayer acrylic polymer.
- the multilayer acrylic polymer may be in the form of powder, granules, aggregates, or coagulum.
- the coagulated material of the present invention preferably has a bulk density of 0.3 to 0.6 g / cm 3 , more preferably 0.35 to 0.55 g / cm 3 , still more preferably 0.4 to 0. 5g / cm 3 It is.
- the coagulated material of the present invention preferably has a median diameter measured by a light scattering method of 50 to 400 ⁇ m, more preferably 75 to 375 ⁇ m, and still more preferably 100 to 350 ⁇ m. The smaller the median diameter, the worse the processability, and the larger the median diameter, the lower the quality.
- the ratio of particles having a particle diameter of 75 ⁇ m or less measured by light scattering method is preferably 50% or less, more preferably 40% or less, and still more preferably 30% or less.
- the measurement of the median diameter and the particle diameter by the light scattering method can be performed, for example, by using a particle diameter distribution measuring apparatus LA-950V2 manufactured by Horiba, Ltd., whose measurement method is a laser diffraction / scattering type.
- the coagulated substance of the present invention has a parameter represented by the following formula (1A)
- N amount of alkali metal and alkaline earth metal contained in the coagulated substance (mmoL / kg), Tg; glass transition temperature of acetone solubles (° C.) a: The valence number of the alkali metal and the alkaline earth metal contained in the coagulated product is preferably 100 or less, more preferably 90 or less, and still more preferably 80 or less. The smaller the parameter represented by the formula (1A), the better the hot water resistance or boiling water whitening resistance of the film obtained from the coagulated substance tends to be improved.
- alkali metals include sodium, potassium, lithium, rubidium and cesium
- alkali metals to be measured in relation to the formula (1) are preferably sodium and potassium
- the alkaline earth metals include magnesium, calcium, strontium and barium, but the alkaline earth metals measured in relation to the formula (1) are preferably magnesium and calcium.
- the acetone soluble matter and the acetone insoluble matter of the coagulated material of the present invention can be measured as follows. That is, 2 g of the coagulated product of the present invention is added to 50 mL of acetone and stirred at room temperature for 24 hours, and the total amount of the obtained solution is subjected to conditions of rotational speed 20000 rpm and temperature 0 ° C. for 180 minutes using a centrifuge. The supernatant and the precipitate are separated by centrifugation, dried at 50 ° C.
- acetone solubles obtained by evaporating acetone from the supernatant
- acetone insolubles precipitates
- the acetone insolubles are present inside the multilayer acrylic polymer, and the acetone solubles are present outside or on the surface of the multilayer acrylic polymer.
- the shell layer is composed of an acetone soluble component, or an acetone soluble component is a main component and the core layer is acetone It is composed of insoluble matter, or acetone insoluble matter is the main component.
- the core layer is composed of an acetone insoluble component, or an acetone insoluble component is a main component
- an outer shell layer Is composed of acetone soluble, or acetone soluble is the main component
- the inner shell layer may be composed of acetone soluble, acetone insoluble may be composed, acetone soluble Both minute and acetone insolubles may be contained in any proportion.
- a preferred inner shell layer is composed of an acetone insoluble component, or an acetone insoluble component is a main component.
- the number of layers of the multilayer acrylic polymer is 2 to 5, preferably 2 to 4, particularly preferably 3.
- the outermost layer is composed of acetone soluble components, or acetone soluble components are the main components
- the core layer is composed of acetone insoluble components
- acetone insoluble matter is the main component
- at least one intermediate layer between them may be constituted from acetone soluble matter, may be constituted from acetone insoluble matter, acetone soluble matter and acetone insoluble matter Both minutes may be included in any proportion.
- the multilayer acrylic polymer is composed of an acetone soluble component and an acetone insoluble component.
- the acetone soluble component is preferably composed of a structural unit derived from methyl methacrylate and a structural unit derived from an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, and the alkyl group further has 2 to 2 carbon atoms
- the alkyl methacrylate which is 8 may be included.
- the preferred acetone-soluble matter comprises 80 to 99% by mass of structural units derived from methyl methacrylate, and 1 to 20% by mass of structural units derived from alkyl acrylates having 1 to 8 carbon atoms in the alkyl group.
- the glass transition temperature of the polymer constituting the acetone solubles is preferably 80 to 110 ° C., and more preferably 80 to 100 ° C. or 90 to 110 ° C.
- the insoluble matter in acetone is a structural unit derived from methyl methacrylate, a structural unit derived from an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group, a structural unit derived from a crosslinking agent and / or a grafting agent, copolymerizable It may contain structural units derived from other monomers.
- the preferred acetone insolubles are 20 to 60% by mass, preferably 40 to 60% by mass, of structural units derived from methyl methacrylate, and 40 to 80% by mass of structural units derived from alkyl acrylates having 1 to 8 carbon atoms in the alkyl group. , Preferably 40 to 60% by mass, and 0 to 20% by mass of vinyl monomers copolymerizable therewith.
- the glass transition temperature of the polymer constituting the acetone insoluble matter is preferably 0 ° C. or less.
- a core-shell multilayer structure is preferable.
- the core-shell multilayer structure acrylic polymer is obtained, for example, by melt-kneading a three-layer granular body composed of a core, an inner shell and an outer shell.
- the core and the inner shell, and the inner shell and the outer shell are composed of different polymers. It is preferable that the core and the inner shell, and the inner shell and the outer shell be in contact without any gap.
- the polymer constituting the inner shell is preferably softer than the polymer constituting the core and the polymer constituting the outer shell.
- the polymer constituting the inner shell and the polymer constituting the core are preferably insoluble in acetone.
- the polymer constituting the outer shell is preferably soluble in acetone.
- the polymer constituting the outer shell may be a matrix of two-layer particles consisting of a core and an inner shell when all or a part of the outer shell is fused by melt-kneading the three-layer particles.
- the lower limit of the average particle diameter of the three-layer granular body contained in the core-shell multilayer structure acrylic polymer coagulated substance is preferably 0.01 ⁇ m, more preferably 0.04 ⁇ m, still more preferably 0.05 ⁇ m, still more preferably 0
- the upper limit of the average particle size is preferably 0.35 ⁇ m, more preferably 0.3 ⁇ m, still more preferably 0.2 ⁇ m, still more preferably 0.15 ⁇ m.
- the stress whitening resistance of the film tends to decrease as the average particle size of the particles is larger.
- the average particle diameter of the three-layered particles is a value obtained by light scattering method.
- the coagulated product of the present invention is obtained by aggregating (the first coagulating step) and granulating (the second coagulating step) the latex (core-shell multilayer structure acrylic polymer or three-layered particles) obtained by the polymerization reaction.
- the median size of the coagulated substance obtained is 50 to 400 ⁇ m, and the ratio of particles having a particle size of 75 ⁇ m or less is 50% or less.
- the hard polymer (a) constitutes a core
- the crosslinked rubber polymer (b) constitutes an inner shell
- the hard polymer (c) constitutes an outer shell More preferable.
- a single-layer acrylic polymer consisting of only the hard polymer (c) is used in combination with the acrylic polymer coagulated product. It is also good.
- the hard polymer (a) is a structural unit derived from methyl methacrylate, a structural unit derived from alkyl acrylate, and a structural unit derived from a grafting agent, and, optionally, a structural unit derived from a crosslinking agent and copolymerizable Polymers composed of structural units derived from other monomers.
- the amount of structural units derived from methyl methacrylate in the hard polymer (a) is preferably 40 to 98.99% by mass, more preferably 90 to 96.9% by weight, based on the total structural units of the hard polymer (a). It is mass%.
- the amount of structural units derived from alkyl acrylate in the hard polymer (a) is preferably 1 to 60% by mass, more preferably 3 to 10% by mass, based on all structural units of the hard polymer (a). .
- the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of structural units derived from alkyl acrylates, the lower the thermal decomposition resistance of the multilayer acrylic polymer tends to decrease, and the larger the amount of structural units derived from alkyl acrylates, the hot water resistance or boiling water resistance of the film Tend to decrease.
- the amount of structural units derived from the grafting agent in the hard polymer (a) is preferably 0.01 to 1% by mass, more preferably 0.1 to 1% by weight, based on the total structural units of the hard polymer (a). It is 0.5 mass%. As the amount of structural units derived from the grafting agent decreases, the bonding strength between the hard polymer (a) and the crosslinked rubber polymer (b) tends to decrease, and the amount of structural units derived from the grafting agent increases. There is a tendency that the impact resistance of the film decreases.
- the amount of structural units derived from the crosslinking agent in the hard polymer (a) is preferably 0 to 0.5% by mass, more preferably 0 to 0.2 based on the total structural units of the hard polymer (a). It is mass%. As the amount of structural units derived from the crosslinking agent increases, the impact resistance of the film tends to decrease.
- the amount of structural units derived from other copolymerizable monomers in the hard polymer (a) is preferably 0 to 20% by mass, more preferably the total structural units of the hard polymer (a). It is 0 to 10% by mass.
- the crosslinked rubber polymer (b) is a structural unit derived from an alkyl acrylate, and a structural unit derived from a grafting agent, and, optionally, a structural unit derived from methyl methacrylate, It is a polymer comprising a structural unit derived from a crosslinking agent and a structural unit derived from another copolymerizable monomer.
- the amount of structural units derived from alkyl acrylate in the crosslinked rubber polymer (b) is preferably 70 to 99.5% by mass, more preferably 80 to 99 based on the total structural units of the crosslinked rubber polymer (b). It is mass%.
- the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of structural units derived from alkyl acrylate, the lower the impact resistance of the film tends to be, and the larger the amount of structural units derived from alkyl acrylate, the smaller the stress whitening resistance and transparency of the film tend to be. is there.
- the amount of the structural unit derived from the grafting agent in the crosslinked rubber polymer (b) is preferably 0.5 to 5% by mass, more preferably 1 to 5 based on the total structural units of the crosslinked rubber polymer (b). It is 3% by mass. The smaller the amount of structural units derived from the grafting agent, the lower the stress whitening resistance of the film, and the larger the amount of structural units derived from the grafting agent, the lower the impact resistance of the film. .
- the amount of structural units derived from methyl methacrylate in the crosslinked rubber polymer (b) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, based on the total structural units of the crosslinked rubber polymer (b). It is. As the amount of structural units derived from methyl methacrylate increases, the impact resistance of the film tends to decrease.
- the amount of structural units derived from the crosslinking agent in the crosslinked rubber polymer (b) is preferably 0 to 5% by mass, more preferably 0 to 2% by mass, based on the total structural units of the crosslinked rubber polymer (b). It is. As the amount of structural units derived from the crosslinking agent increases, the impact resistance of the film tends to decrease.
- the amount of structural units derived from other copolymerizable monomers in the crosslinked rubber polymer (b) is preferably 0 to 40% by mass, based on the total structural units of the crosslinked rubber polymer (b). Preferably, it is 0 to 30% by mass.
- the rigid polymer (c) is a polymer comprising a structural unit derived from methyl methacrylate and a structural unit derived from an alkyl acrylate.
- the amount of structural units derived from methyl methacrylate in the hard polymer (c) is preferably 80 to 99% by mass, more preferably 95 to 98% by mass, based on all structural units of the hard polymer (c). .
- the amount of structural units derived from alkyl acrylate in the hard polymer (c) is preferably 1 to 20% by mass, more preferably 2 to 5% by mass, based on all structural units of the hard polymer (c). .
- the alkyl group in the alkyl acrylate preferably has 1 to 8 carbon atoms. The smaller the amount of structural units derived from alkyl acrylate, the lower the thermal decomposition resistance of the multilayer acrylic polymer tends to decrease, and the larger the amount of structural units derived from alkyl acrylate, the lower the stress whitening resistance of the film. Tend.
- the hard polymer (c) has a glass transition temperature of preferably 80 ° C. or more, more preferably 90 ° C. or more, still more preferably 100 ° C. or more. As the glass transition temperature of the hard polymer (c) is higher, the hot water resistance or the boil-off water whitening resistance of the film tends to be improved.
- alkyl acrylate used for the hard polymer (a), the crosslinked rubber polymer (b) and the hard polymer (c) include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, s-butyl Acrylate, t-butyl acrylate, n-butyl methyl acrylate, n-heptyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate and the like can be mentioned.
- These alkyl acrylates can be used singly or in combination of two or more. Of these, methyl acrylate and / or n-butyl acrylate are preferred.
- the grafting agent used for the hard polymer (a) and the crosslinked rubber polymer (b) comprises the hard polymer (a) and the crosslinked rubber polymer (b) and the crosslinked rubber polymer (b) and the hard polymer ( and c) a monomer which is considered to have a role of mainly chemically bonding with c) and a role of assisting the formation of a crosslinked structure in the hard polymer (a) or the crosslinked rubber polymer (b).
- the grafting agent is a monomer having two or more different kinds of polymerizable groups.
- examples of the grafting agent include allyl methacrylate, allyl acrylate, mono- or di-allyl maleate, mono- or di-allyl fumarate, crotyl acrylate, crotyl methacrylate and the like. These grafting agents can be used singly or in combination of two or more.
- allyl methacrylate improves the bonding ability between the hard polymer (a) and the crosslinked rubber polymer (b) or between the crosslinked rubber polymer (b) and the hard polymer (c). It is preferably used because it is excellent in the effect of improving the stress whitening resistance and the transparency of the film.
- the crosslinking agent used for the hard polymer (a) and the crosslinked rubber polymer (b) is considered to mainly have a role of forming a crosslinked structure in the hard polymer (a) or the crosslinked rubber polymer (b) It is a monomer.
- the crosslinking agent is a monomer having two or more polymerizable groups of the same type, and examples thereof include diacrylic compounds, dimethacrylic compounds, diallyl compounds, divinyl compounds, diene compounds, trivinyl compounds and the like.
- a crosslinking agent for example, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, divinyl benzene, trivinyl benzene, ethylene glycol diaryl ether And propylene glycol diallyl ether, butadiene and the like.
- These crosslinking agents can be used singly or in combination of two or more.
- the hard polymer (a) and the other polymerizable monomer used for the crosslinked rubber polymer (b) may be any vinyl-based monomer copolymerizable with methacrylic acid ester, for example, Aromatic vinyl monomers such as styrene, p-methylstyrene, o-methylstyrene and vinylnaphthalene, unsaturated nitrile monomers such as acrylonitrile, olefin monomers such as ethylene and propylene, vinyl chloride and vinylidene chloride , Halogenated vinyl monomers such as vinylidene fluoride, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid and maleic anhydride, vinyl acetate, N-propyl maleimide, N-cyclohexyl maleimide, N-o And maleimide monomers such as -chlorophenyl maleimide, and these compounds may be used alone or in combination. It can be used in combination of at least.
- the coagulated product of the present invention has a melt flow rate at 230 ° C. under a load of 3.8 kg of preferably 0.5 to 20 g / 10 min, more preferably 0.8 to 10 g / 10 min.
- a melt flow rate of the multilayer acrylic polymer decreases, the flowability of the multilayer acrylic polymer and the formability of the film tend to decrease.
- the higher the melt flow rate of the multilayer acrylic polymer the lower the mechanical properties of the film.
- the acetone soluble matter and the acetone insoluble matter can be measured as follows.
- acetone solubles and the acetone insolubles can be measured by measuring their mass.
- the acetone-soluble component of the acrylic polymer coagulated product is 80 to 99% by mass of a structural unit derived from methyl methacrylate, and an alkyl acrylate having 1 to 8 carbon atoms in the alkyl group. Containing 1 to 20% by mass of a structural unit derived from the following, having a glass transition temperature of 80 to 110 ° C., preferably 80 to 100 ° C., or 90 to 110 ° C.
- the coagulated acrylic polymer has an acid value of preferably not more than 0.008 mmol / g, more preferably not more than 0.006 mmol / g, still more preferably 0. It is 004 mmol / g or less.
- the lower limit of the acid value of the acetone insoluble matter of the multilayer acrylic polymer is preferably 0.001 mmol / g. As the acid value of the acetone insoluble portion of the multilayer acrylic polymer is lower, the hot water resistance or the boil-off water whitening resistance of the film tends to be improved.
- the multilayer acrylic polymer used in the present invention preferably has an acid value of 0.012 mmol / g or less, more preferably 0.009 mmol / g or less, as an acetone soluble matter. More preferably, it is 0.007 mmol / g or less.
- the lower limit of the acid value of the acetone soluble matter of the multilayer acrylic polymer is preferably 0.001 mmol / g. The lower the acid value of the multilayer acrylic polymer, the better the hot water resistance or boiling water whitening resistance of the film tends to be.
- the polymer chains of the hard polymer (a), the cross-linked rubber polymer (b), and the hard polymer (c) grafted to the polymer chains of the cross-linked rubber polymer (b) are acetone insolubles Is detected as The polymer chain of the hard polymer (c) which is not graft-bonded to the polymer chain of the crosslinked rubber polymer (b) is detected as an acetone soluble component.
- the method for producing the multilayer acrylic polymer is not particularly limited.
- a hard polymer (a), a crosslinked rubber polymer (b), and a hard polymer (c) can be formed sequentially by seed emulsion polymerization to obtain an acrylic polymer having a core-shell multilayer structure.
- emulsion polymerization of acrylic monomers is carried out to obtain a latex containing a multilayer acrylic polymer; and a latex containing a multilayer acrylic polymer is coagulated to be a slurry. Washing and dewatering the slurry; and drying the dewatered slurry.
- More preferable production method of the coagulated product of the present invention is as follows: methyl methacrylate 40 to 98.99% by mass, more preferably 90 to 96.9% by mass and alkyl group having 1 to 8 carbon atoms in the presence of an emulsifier Alkyl acrylate 1 to 60% by mass, more preferably 3 to 10% by mass, grafting agent 0.01 to 1% by mass, more preferably 0.1 to 0.5% by mass and crosslinking agent 0 to 0.5% by mass More preferably 0 to 0.2% by mass (1st polymerization) to obtain a latex (I) containing a hard polymer (a); and in the presence of the latex (I), the carbon number of the alkyl group is 70 to 99.5% by mass, more preferably 80 to 99% by mass, 1 to 8 of alkyl acrylate, 0 to 30% by mass of methyl methacrylate, more preferably 0 to 20% by mass, 0.5 to 5% of a grafting agent %, More preferred 1 to 3%
- the polymerization can be carried out by known methods. Of the polymerizations carried out in the presence of a latex, seed emulsion polymerization is preferably used to obtain a core-shell multilayer acrylic polymer. Emulsion polymerization, or seed polymerization, can be carried out according to a conventional method, as it is a method well known in the art.
- the reaction system is a mixture of monomers used in each polymerization, specifically methyl methacrylate, alkyl acrylate, other copolymerizable monomers, a grafting agent and a crosslinking agent in the above-mentioned proportions.
- the feed rate is preferably 0.05 to 3% by mass, more preferably 0.1 to 1% by mass, based on 100% by mass of the total amount of monomers used in each polymerization.
- Min more preferably 0.2 to 0.8% by mass / min.
- the polymerization initiator used in each polymerization is not particularly limited.
- the polymerization initiator include: water-soluble inorganic initiators such as potassium persulfate and ammonium persulfate; redox initiators obtained by using an inorganic initiator in combination with sulfites or thiosulfates; organic peroxides Examples thereof include redox initiators formed by using ferrous salts or sodium sulfoxylate in combination.
- the polymerization initiator may be added collectively to the reaction system at the start of the polymerization, or may be divided into the polymerization start and the middle of the polymerization and added to the reaction system in consideration of the reaction rate and the like.
- the use amount of the polymerization initiator can be appropriately set, for example, so that the average particle diameter of the particles contained in the core-shell multilayer structure acrylic polymer falls within the above-mentioned range.
- the emulsifier used in each polymerization is not particularly limited.
- the emulsifier include anionic emulsifiers such as long chain alkyl sulfonates, sulfosuccinic acid alkyl ester salts and alkyl benzene sulfonates; nonionic emulsifiers such as polyoxyethylene alkyl ethers and polyoxyethylene nonyl phenyl ethers; Nonylphenylether sodium sulfate, etc.
- Nonylphenylether sulfate Polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene alkylether sulfate, Polyoxyethylene alkyl ether sulfate such as sodium polyoxyethylene tridecyl ether acetate, etc. Mention may be made of nonionic and anionic emulsifiers. The amount of the emulsifier used can be appropriately set so that, for example, the average particle diameter of the particles contained in the core-shell multilayer structure acrylic polymer falls within the range described above.
- the 1st polymerization, the 2nd polymerization and the 3rd polymerization may be sequentially performed in one polymerization tank, or the polymerization tank may be changed every time the 1st polymerization, 2nd polymerization and 3rd polymerization.
- each polymerization is preferably carried out sequentially in one polymerization tank.
- the temperature of the reaction system during polymerization is preferably 30 to 120 ° C., more preferably 50 to 100 ° C.
- a reactive ultraviolet absorber for example, 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] -2H-1, 2,3-Benzotriazole etc.
- the reactive ultraviolet absorber is introduced into the molecular chain of the multilayer acrylic polymer, and the ultraviolet resistance of the multilayer acrylic polymer is improved.
- the addition amount of the reactive UV absorber is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of monomers used for polymerization.
- Chain transfer agents can be used in each polymerization to control molecular weight.
- the melt flow rate of a multilayer structure acrylic polymer can be made into the above-mentioned range by adding a chain transfer agent to a reaction system, and adjusting the molecular weight of a hard polymer (c).
- the chain transfer agent used for each polymerization is not particularly limited.
- chain transfer agents examples include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and n-hexadecyl mercaptan; xanthogen disulfides such as dimethyl xanthogen disulfide and diethyl xanthogen disulfide; And thiuram disulfides; and halogenated hydrocarbons such as carbon tetrachloride and ethylene bromide.
- the use amount of the chain transfer agent can be appropriately set within a range in which the polymer can be adjusted to a predetermined molecular weight in each polymerization.
- the amount of chain transfer agent used in the 3rd polymerization is such that the value of the melt flow rate can be in the aforementioned range.
- the amount of chain transfer agent used in the 3rd polymerization varies depending on the amount of polymerization initiator used in the 3rd polymerization, etc., but the total amount of monomers used in the 3rd polymerization, specifically methyl methacrylate and alkyl acrylate
- the amount is preferably 0.05 to 2 parts by mass, more preferably 0.08 to 1 parts by mass with respect to 100 parts by mass.
- the recovery of the multilayer acrylic polymer from the emulsion latex is carried out by coagulating the emulsion latex.
- the coagulation of the latex can be carried out by known methods. Examples of the coagulation method include freeze coagulation, salting out coagulation, acid precipitation coagulation and the like. Among these, the salting-out coagulation method which can continuously produce high quality coagulum is preferable.
- the coagulant which can be used in the present invention may be an aqueous solution of an inorganic acid or a salt thereof having the property of coagulating and coagulating the emulsion polymerization latex, or an organic acid or a salt thereof.
- inorganic acid solution inorganic acid salt solution, organic acid solution or organic acid salt solution
- Alkali metal halides such as potassium iodide and sodium iodide
- alkali metal sulfates such as potassium sulfate and sodium sulfate
- ammonium sulfate ammonium chloride
- alkali metal nitrates such as sodium nitrate and potassium nitrate
- Aqueous solutions of inorganic salts such as calcium acetate, zinc sulfate, copper sulfate, barium chloride, ferrous chloride, ferric chloride, magnesium chloride, ferric sulfate, aluminum sulfate, potassium alum and iron alum alone or in combination And mixtures thereof.
- aqueous solutions of salts of monovalent or divalent inorganic acids such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, calcium acetate and the like can be suitably used.
- salts of monovalent or divalent inorganic acids such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, calcium acetate and the like can be suitably used.
- salts of monovalent or divalent inorganic acids such as sodium chloride, potassium chloride, sodium sulfate, ammonium chloride, calcium chloride, magnesium chloride, magnesium sulfate, barium chloride, calcium acetate and the like.
- the emulsion latex is a multilayer structure acrylic polymer latex consisting of a hard polymer (a), a crosslinked rubber polymer (b), and a hard polymer (c) alone or a mixture of two or more, or a hard polymer ( a) adding a coagulant to a mixture of a multilayer acrylic polymer latex comprising a crosslinked rubber polymer (b) and a hard polymer (c) and at least one single-layer acrylic polymer latex Can be solidified.
- the first coagulation (flocculation step) is a reaction in which loose aggregation is performed, and the emulsified latex and the coagulant solution are mixed while being heated, and aggregation is allowed to proceed at a moderate speed.
- the polymer concentration of the emulsion latex in the first coagulation (flocculation step) is preferably 5 to 25% by mass, more preferably 7.5 to 22.5% by mass, and still more preferably 10 to 20% by mass. .
- the polymer concentration of the emulsion latex is lower, aggregation is more difficult to proceed, and as it is higher, aggregation is more likely to proceed, but there is a tendency for control to be difficult due to the high viscosity.
- the addition concentration of the coagulant in the first coagulation (flocculation step) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 7.5 parts by mass, with respect to 100 parts by mass of the polymer in the emulsion latex. More preferably, it is 1.0 to 5.0 parts by mass.
- the addition concentration of the coagulant is low, the aggregation is difficult to progress, and the aggregation tends to progress as the concentration is high, but the hot water resistance or the boiling water whitening resistance of the obtained coagulant tends to be deteriorated.
- the liquid temperature in the first coagulation (aggregation step) is preferably 60 to 90 ° C., more preferably 65 to 85 ° C., still more preferably 70 to 80 ° C.
- the residence time in the first coagulation (flocculation step) is preferably 0.25 to 2.0 hours, more preferably 0.5 to 1.75 hours, still more preferably 0.75 to 1.5 hours. As the residence time is shorter, the particle size of the coagulated material obtained is insufficient due to insufficient aggregation, and the aggregation tends to proceed more easily as the residence time is longer, but the hot water resistance or the boiling water whitening resistance of the obtained coagulated material tends to deteriorate.
- the second coagulation (granulation step) is to further heat the slurry obtained in the first coagulation (aggregation step) to reduce fine particles which are not aggregated and to increase the bulk density of the coagulated substance.
- the concentration of the polymer can be adjusted by adding ion-exchanged water to the slurry obtained by the aggregation for dilution.
- the polymer concentration of the diluted slurry is preferably 1 to 20% by mass, more preferably 3 to 17.5% by mass, and still more preferably 5 to 15% by mass. The lower the polymer concentration of the emulsion latex, the more difficult the granulation proceeds, and the higher the concentration, the easier the granulation proceeds, but the hot water resistance or the boil-off water whitening resistance of the coagulated product tends to deteriorate.
- the liquid temperature in the second coagulation (granulation step) is preferably 80 to 110 ° C., more preferably 85 to 105 ° C., and still more preferably 90 to 100 ° C.
- the residence time in the second coagulation (granulation step) is preferably 0.25 to 2.0 hours, more preferably 0.5 to 1.75 hours, still more preferably 0.75 to 1.5 hours. As the residence time is shorter, granulation is insufficient and the particle size of the obtained coagulated material is smaller. As the residence time is longer, granulation tends to proceed, but the hot water resistance or boiling water resistance of the obtained coagulated material tends to be deteriorated.
- washing and dewatering of the slurry obtained by coagulation be sufficiently performed so that the alkali metal and alkaline earth metal contained in the coagulation fall within the above-mentioned range.
- water soluble components represented by a coagulant can be removed from the slurry.
- the washing and dewatering of the slurry can be performed, for example, with a filter press, a belt press, a gear type centrifuge, a screw decanter type centrifuge, or the like. It is preferable to use a screw decanter centrifuge from the viewpoint of productivity and cleaning efficiency.
- the washing and dewatering of the slurry are preferably performed at least twice. The higher the number of washings and dehydrations, the lower the residual amount of the water soluble component. However, from the viewpoint of productivity, the number of washing and dehydration is preferably three or less.
- the water content of the coagulated substance after dehydration is preferably 5 to 50% by mass, more preferably 5 to 45% by mass, and still more preferably 5 to 40% by mass. As the water content is higher, the drying can not be sufficiently performed, and it becomes difficult to obtain a coagulated material having a suitable water content after drying.
- the turbidity of the waste water discharged at the time of dehydration is preferably 1000 or less, more preferably 700 or less, and still more preferably 400 or less.
- the turbidity of the drainage is high, it indicates that the solid-liquid separation property is insufficient, and not only the product yield is lowered, but also it causes difficulties such as clogging of the discharge pump strainer and it becomes difficult to operate stably.
- Drying of the coagulum is carried out such that the water content is preferably less than 0.2% by weight, more preferably less than 0.1% by weight.
- the higher the water content the more likely the ester hydrolysis reaction occurs in the multilayer acrylic polymer during melt-extrusion and the formation of carboxyl groups in the molecular chain.
- the coagulated material has an acid value of acetone insolubles of 0.018 mmol / g or less, preferably 0.015 mmol / g or less, more preferably 0.012 mmol / g or less.
- the lower limit of the acid value of the acetone insoluble matter of the coagulated product is preferably 0.001 mmol / g. As the acid value of the acetone insoluble portion of the coagulated product is lower, the hot water resistance or the boil-off water whitening resistance of the film tends to improve.
- the coagulated product has an acid value of 0.012 mmol / g or less, preferably 0.009 mmol / g or less, more preferably 0.007 mmol / g or less in acetone solubles .
- the lower limit of the acid value of the acetone soluble portion of the coagulated product is preferably 0.001 mmol / g. The lower the acid value of the acetone-soluble matter of the coagulated substance, the better the hot water resistance or boiling water whitening resistance of the film tends to be improved.
- the coagulant has a glass transition temperature of preferably 80 ° C. or more, more preferably 90 ° C. or more, still more preferably 100 ° C. or more.
- the coagulated substance of the present invention may be mixed with another thermoplastic resin and extruded.
- Other thermoplastic resins include polycarbonate polymers, vinyl chloride polymers, vinylidene fluoride polymers, vinyl acetate polymers, maleic acid copolymers, acrylic resins, ABS resins, AES resins, AS resins And the like.
- the weight ratio of the other thermoplastic resin / coagulate is preferably 0/100 to 35/65, more preferably 0/100 to 20/80.
- the coagulated material of the present invention may be mixed with an acrylic resin and extruded.
- the mass ratio of acrylic resin / coagulate is preferably 0/100 to 35/65, more preferably 0/100 to 20/80. If it is this range, film forming property will become good.
- Acrylic resin which can be used as needed in extrusion molding is resin which has a structural unit derived from methyl methacrylate and a structural unit derived from an acrylic ester as needed.
- the amount of structural units derived from methyl methacrylate in the acrylic resin is preferably 85 to 100% by mass, and more preferably 92 to 100% by mass, based on the mass of all structural units of the acrylic resin.
- the amount of the structural unit derived from the acrylic ester in the acrylic resin is preferably 0 to 15% by mass, more preferably 0 to 8% by mass, based on the mass of all the structural units of the acrylic resin.
- acrylic acid ester in acrylic resin methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, s-butyl acrylate, t-butyl acrylate, amyl acrylate, isoamyl acrylate, n- Hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, cyclohexyl acrylate, norbornenyl acrylate, isobonyl acrylate, benzyl acrylate, phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate , Glycidyl acrylate, allyl acrylate, phenyl acrylate, etc. Can.
- the acrylic resin used for extrusion molding as required has a glass transition temperature of preferably 95 ° C. or more, more preferably 100 ° C. or more, still more preferably 105 ° C. or more.
- the acrylic resin preferably has a melt flow rate at a temperature of 230 ° C. under a load of 3.8 kg of 0.5 to 20 g / 10 min, more preferably 0.8 to 10 g / 10 min.
- the said acrylic resin is not restrict
- it can manufacture by well-known polymerization methods, such as a radical polymerization method and an anion polymerization method.
- the adjustment of the acrylic resin to the above-mentioned characteristic values is carried out by adjusting the polymerization conditions, specifically, the polymerization temperature, the polymerization time, the kind and amount of chain transfer agent, the kind and amount of the polymerization initiator, etc. You can do this by Adjustment of the resin properties by adjusting such polymerization conditions is a technique well known to those skilled in the art.
- the coagulated material and the acrylic resin are preferably pelletized to facilitate transportation, storage, molding and the like. It is preferable that the extruder used when pelletizing a multilayer structure acrylic polymer is equipped with a vent.
- the vent is preferably a vacuum vent or an open vent. Preferably, at least one vent is provided downstream of the resin melting start portion.
- the pressure in the vacuum vent is preferably 30 Torr or less, more preferably 15 Torr or less, still more preferably 9 Torr or less, and most preferably 6 Torr or less. If the pressure in the vacuum vent is within the above range, the degassing efficiency is good, and the residual water and monomers can be reduced.
- the extruder used for pelletizing is preferably a single screw system.
- the single screw extruder has a small shearing energy to be applied to the multilayer acrylic polymer and the like, and can suppress the thermal decomposition of the polymer.
- the screw configuration is preferably full flight.
- the cylinder heating temperature of the extruder used for pelletizing is preferably 210 to 270 ° C., more preferably 220 to 260 ° C., and still more preferably 230 to 250 ° C.
- the residence time in the extruder is preferably 7 minutes or less, more preferably 5 minutes or less, still more preferably 3 minutes or less. The higher the cylinder heating temperature or the longer the residence time, the larger the shear energy given to the multilayer acrylic polymer and the like, the thermal decomposition of the polymer tends to progress, and the hot water whitening resistance of the film tends to decrease.
- the water content of the multilayer acrylic polymer and the acrylic resin before being subjected to extrusion molding is preferably less than 0.2% by mass, more preferably less than 0.1% by mass. As the water content is higher, silver streaks are likely to occur and the resistance to hot water whitening may deteriorate.
- Additives to coagulants and acrylic resins if necessary, for known resins such as UV absorbers, antioxidants, light stabilizers, anti-aging agents, plasticizers, polymer processing aids, lubricants, dyes and pigments
- An agent may be included.
- the total content of the resin additive is preferably 20% by mass or less based on 100% by mass of the total amount of the coagulated product and the acrylic resin.
- the additive for resin may be added, for example, to a coagulated substance and acrylic resin melted in a film molding machine, or may be dry blended to a pelletized coagulated substance or acrylic resin, or coagulated. Or acrylic resin may be added when pelletizing (master batch method).
- the coagulated material and the acrylic resin contain an ultraviolet absorber.
- UV absorbers include reactive UV absorbers such as 2- [2-hydroxy-5- (2-methacryloyloxyethyl) phenyl] -2H-1,2,3-benzotriazole.
- the content of the ultraviolet absorber is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the total amount of the coagulated product and the acrylic resin.
- the coagulated product of the present invention When used as a molded product, it can be molded into a plate, a film or the like by a general molding method such as heat melting and extrusion molding, injection molding or the like.
- the extruder used for film formation preferably comprises a vent.
- the vent is preferably a vacuum vent or an open vent.
- at least one vent is provided downstream of the resin melting start portion.
- the pressure in the vacuum vent is preferably 30 Torr or less, more preferably 15 Torr or less, still more preferably 9 Torr or less, and most preferably 6 Torr or less.
- the extruder used for film formation is preferably a single screw system or a co-rotating twin screw system.
- the cylinder heating temperature of the extruder used for film formation is preferably 220 to 300 ° C., more preferably 230 to 290 ° C., and still more preferably 240 to 280 ° C.
- the residence time in the extruder used for film formation is preferably 7 minutes or less, more preferably 5 minutes or less, still more preferably 3 minutes or less.
- the higher the cylinder heating temperature or the longer the residence time the larger the shear energy given to the multilayer acrylic polymer and the like, the thermal decomposition of the polymer tends to progress, and the hot water whitening resistance of the film tends to decrease. Therefore, it is preferable that extrusion for film formation is performed with a residence time in an extruder of 5 minutes or less and a resin temperature of 280 ° C. or less.
- the resin film obtained from the coagulated product of the present invention is excellent in impact resistance, is excellent in stress whitening resistance, does not cause whitening even when bent, is excellent in warm water whitening resistance and boiling water resistant white water resistance, and is warm water and Even if exposed to boiling water, whitening does not occur.
- the resin film obtained from the coagulated product of the present invention is also excellent in adhesion to other polymers, particularly thermoplastic polymers.
- the resin film obtained from the coagulated product of the present invention preferably has a thickness of 10 to 500 ⁇ m, more preferably 20 to 400 ⁇ m, and still more preferably 30 to 300 ⁇ m.
- the resin film obtained from the coagulated product according to the preferred embodiment of the present invention preferably has a haze (H 0 ) of 1.5% or less, more preferably 1% or less, still more preferably 0.5% or less, at normal temperature storage It is.
- the haze is measured with a test piece having an optical path length of 200 ⁇ m in accordance with JIS K7136.
- the resin film obtained from the coagulated product of the preferred embodiment of the present invention has a haze change width ( ⁇ H 80 ) of preferably 10% or less, more preferably 7% or less before and after the hot water resistance whitening test using water at 80 ° C. More preferably, it is 5% or less.
- the resin film has a haze change width ( ⁇ H 100 ) of preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less before and after the boiling water whitening test using 100 ° C. water (boiling water). is there.
- the laminate of the present invention has at least one layer of the resin film of the present invention and at least one layer of another thermoplastic polymer.
- thermoplastic polymers used in the laminate of the present invention are not particularly limited.
- Other thermoplastic polymers include polycarbonate polymers, vinyl chloride polymers, vinylidene fluoride polymers, vinyl acetate polymers, maleic acid copolymers, methacrylic resins, ABS resins, AES resins, or AS Resin is preferable because of its good adhesion to the resin film of the present invention.
- the thermoplastic polymer molded article may be a planar molded article such as a film, a sheet, or a plate, or may be a linear molded article such as a tube or a rod, or a lens, a prism, a container, etc. It may be a molded article of various shapes such as.
- the laminate of the present invention is not particularly limited by the production method thereof.
- the laminate is, for example, coated with the above-mentioned multilayer acrylic resin on another thermoplastic polymer molded article by co-extrusion molding of the above-mentioned multilayer acrylic polymer and the other thermoplastic polymer.
- Other thermoplastic polymer moldings by placing other thermoplastic polymer moldings in the desired mold by extrusion molding, melting the multilayer acrylic polymer and injecting or injecting into said mold It can be obtained by placing the above-mentioned multilayer structure acrylic resin on an article and pressing it, or by thermally fusing or bonding the resin film of the present invention to another thermoplastic polymer molded article.
- the slurry before dehydration of the latex of the multilayer acrylic polymer or the coagulated acrylic polymer is collected, and it is measured by a light scattering method using a laser diffraction / scattering particle size distribution analyzer LA-910 manufactured by Horiba, Ltd. The average particle size was determined.
- melt flow rate The melt flow rate (hereinafter referred to as “MFR”) at a load of 3.8 kg at 230 ° C. was measured according to ASTM-D1238.
- Glass-transition temperature In accordance with JIS K7121, using a differential scanning calorimeter (DSC-50, manufactured by Shimadzu Corporation), the temperature is raised once to 250 ° C., and then cooled to room temperature, and then from room temperature to 230 ° C. at 20 ° C./min. The DSC curve was measured under the conditions of temperature rise. The midpoint glass transition temperature determined from the DSC curve is referred to as the glass transition temperature (hereinafter referred to as "Tg") in the present invention.
- Tg glass transition temperature
- the turbidity of the waste water after centrifugation in the first washing was measured by the transmission light turbidity method according to JIS K 0101.
- the bulk density Place approximately 5 g of the coagulated powder which has been weighed into a dry 10 mL measuring cylinder without compacting. Carefully flatten the top of the powder layer without compacting and read the loose bulk volume (V) to the smallest scale unit.
- the bulk density (g / cm 3 ) was calculated by m / V.
- Haze (H 0 ) was measured at room temperature using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) in accordance with JIS K7136. The specimens were then immersed in water at 100 ° C. for 4 hours. Thereafter, the water droplets adhering to the film surface were removed, and dried in a hot air dryer set at 100 ° C. for 8 hours. The haze was measured while the film was at room temperature. The amount of increase from the haze at room temperature to the haze after immersion in boiling water ( ⁇ H 100 ) was calculated.
- methyl methacrylate is MMA
- n-butyl acrylate is nBA
- methyl acrylate is MA
- styrene is St
- allyl methacrylate is ALMA
- n-octyl mercaptan (chain transfer agent) is nOM
- sodium dodecylbenzene sulfonate is DBSS. I omit and describe, respectively.
- a reactor containing a latex containing a hard polymer (a) 0.030 parts of potassium persulfate was charged and stirred for 5 minutes. Then, a monomer mixture consisting of 4 parts of MMA, 26 parts of nBA and 0.9 parts of ALMA was continuously added dropwise over 40 minutes to perform seed emulsion polymerization. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, and seed emulsion polymerization was performed so as to have a conversion of 98% or more to obtain a latex containing a hard polymer (a) and a crosslinked rubber polymer (b).
- PMMA latex (hereinafter referred to as PMMA latex [1]) was obtained.
- the average particle size of PMMA latex [1] determined by light scattering was 0.09 ⁇ m.
- the monomer unit compositional ratio and the average particle diameter of the PMMA latex [1] are shown in Table 1.
- Example 1 PMMA latex [1] was coagulated under the following conditions.
- An aqueous solution having a ratio of 0.43 parts of magnesium sulfate and 167 parts of ion-exchanged water was heated to 80 ° C., and the above latex was fed at 8.3 parts / minute with stirring for 12 minutes. After completion of the feeding, stirring was continued for 1 hour while maintaining the liquid temperature at 80 ° C. to obtain a coagulated slurry. Further, 267 parts of water was added to the slurry, and the temperature was raised to 90 ° C. and heat treatment was performed for 1 hour to obtain a granulated slurry.
- the obtained granulated slurry was subjected to washing and dewatering of the slurry by a centrifugal force of 2100 G using a screw decanter centrifuge. Subsequently, ion-exchanged water was added to a slurry concentration of 10% by mass, washing and dewatering were again performed with a screw decanter centrifuge, and this operation was repeated a total of three times.
- the water content of the obtained water-containing coagulated material was 37% by mass, the median diameter was 135 ⁇ m, and the ratio of particles having a particle diameter of 75 ⁇ m or less was 22%.
- the dewatered slurry was dried by a continuous fluid bed dryer set at 80 ° C. to obtain a coagulated acrylic polymer.
- the bulk density of the obtained coagulated material was 0.42 g / cm 3 , and the amounts of alkali metal and alkaline earth metal contained were as shown in Table 2.
- the dried acrylic polymer coagulated material has a water content of 0.06% by mass, an MFR of 2.0 g / 10 min, a Tg of 90 ° C., an acid value of acetone insolubles of 0.004 mmol / g, acetone soluble The acid value of the portion was 0.009 mmol / g.
- the dried acrylic polymer coagulated product was heat pressed at 190 ° C. to obtain a resin film of 200 ⁇ m in thickness.
- the resin film had a haze of 0.4%, a ⁇ H 80 of 3%, and a ⁇ H 100 of 17% at room temperature. It can be seen that the hot water whitening resistance and the boiling water whitening resistance are excellent.
- Examples 2 to 9 and Comparative Examples 1 to 4 The same as Example 1 except that the type and amount of PMMA latex used, the amount of water, the type and amount of coagulant, the coagulation time, temperature, and the number of washings / dewatering were changed as described in Table 2 and Table 3.
- An acrylic polymer coagulated product was obtained by the method.
- Comparative Example 2 had a high turbidity with a drain water turbidity of 1040 and a high resin moisture content of 54% by mass after dewatering, and a coagulated product of inferior quality was obtained. Therefore, resin physical properties, metal content, and hot water whitening resistance Test was not conducted.
- Example 10 The latex [1] was frozen by placing it in an atmosphere of ⁇ 20 ° C. for 4 hours.
- the resulting frozen product was poured into three volumes of water at 80 ° C. to which a certain amount of antifoaming agent composed of magnesium sulfate had been added to thaw to obtain a slurry.
- the slurry was washed and dewatered by a centrifugal force of 2100 G using a screw decanter centrifuge. Subsequently, ion-exchanged water was added to a slurry concentration of 10%, and washing and dewatering were performed again using a screw decanter centrifuge.
- the water content of the obtained water-containing coagulated material was 20%, the median diameter was 89 ⁇ m, and the ratio of particles having a particle diameter of 75 ⁇ m or less was 38%.
- the dewatered slurry was dried by a continuous fluid bed dryer set at 80 ° C. to obtain a coagulated acrylic polymer.
- the bulk density of the obtained coagulated material was 0.50 g / cm 3 , and the amounts of alkali metal and alkaline earth metal contained were as shown in Table 2.
- the dried acrylic polymer coagulated material has a moisture content of 0.04% by mass, an MFR of 1.8 g / 10 min, a Tg of 90 ° C., an acid value of acetone insolubles of 0.004 mmol / g, and an acetone soluble The acid value of the portion was 0.009 mmol / g.
- the dried acrylic polymer coagulated product was heat pressed at 190 ° C. to obtain a resin film of 200 ⁇ m in thickness.
- the resin film had a haze of 0.4%, a ⁇ H 80 of 3%, and a ⁇ H 100 of 14% at room temperature.
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Abstract
Description
〔1〕 多層構造アクリル系重合体凝固物であって、嵩密度が0.3~0.6g/cm3、メジアン径が50~400μm、粒子径75μm以下の粒子の比率が50%以下で、かつ含有するアルカリ金属およびアルカリ土類金属が下記式(1)を満たすことを特徴とする多層構造アクリル系重合体凝固物。
Tg;アセトン可溶分のガラス転移温度(℃)
a;凝固物に含有されるアルカリ金属およびアルカリ土類金属の価数。
〔2〕 塩析凝固法により得られる〔1〕に記載の凝固物。
〔3〕 多層構造アクリル系重合体がアセトン可溶分およびアセトン不溶分からなり、アセトン可溶分が、メチルメタクリレートに由来する構造単位80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~20質量%を含み、80~100℃のガラス転移温度を有し、アセトン不溶分がメチルメタクリレートに由来する構造単位20~60質量%、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位40~80質量%を含み、0℃以下のガラス転移温度を有する、〔1〕または〔2〕に記載の凝固物。
〔4〕 多層構造アクリル系重合体がアセトン可溶分およびアセトン不溶分からなり、アセトン可溶分が、メチルメタクリレートに由来する構造単位80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~20質量%を含み、90~110℃のガラス転移温度を有し、アセトン不溶分がメチルメタクリレートに由来する構造単位40~60質量%、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位40~60質量%、およびそれと共重合可能なビニル系単量体0~20質量%を含み、0℃以下のガラス転移温度を有する〔1〕または〔2〕に記載の凝固物。
〔6〕〔1〕~〔4〕に記載のいずれかの凝固物を用いて得られるフィルム。
〔7〕〔1〕~〔4〕に記載のいずれかの凝固物を用いて得られるフィルムからなる少なくとも1つの層と、他の熱可塑性重合体成形品からなる少なくとも1つの層とを有する積層体。
〔8〕以下の工程1~5
工程1:乳化剤の存在下にアクリル系単量体、共重合可能な他の単量体、グラフト化剤および/または架橋剤を重合してラテックス(I)を得る工程、
工程2:ラテックス(I)の存在下にアクリル系単量体、共重合可能な他の単量体、グラフト化剤、任意成分としての架橋剤を重合してラテックス(II)を得る工程、
工程3:ラテックス(II)の存在下にアクリル系単量体を重合してラテックス(III)を得る工程、
工程4:ラテックス(III)を凝固剤の存在下に緩凝集して、多層構造アクリル系重合体の凝集体を得る工程、
工程5:工程4で得られた多層構造アクリル系重合体の凝集体を加熱して、多層構造アクリル系重合体の凝固物を得る工程
を含む、嵩密度が0.3~0.6g/cm3、メジアン径が50~400μm、粒子径75μm以下の粒子の比率が50%以下で、かつ含有するアルカリ金属およびアルカリ土類金属が下記式(1)を満たすことを特徴とする多層構造アクリル系重合体凝固物の製造方法。
Tg;アセトン可溶分のガラス転移温度(℃)
a;凝固物に含有されるアルカリ金属およびアルカリ土類金属の価数。
なお、アクリル系単量体は、メチルメタクリレート、アルキルアクリレートを含むものが好ましい。
である。嵩密度が低いほど工程通過性が悪化し、高いほど品質が悪化する傾向がある。
なお、光散乱法によるメジアン径と粒子径の測定は、例えば、測定方式がレーザー回折/散乱式である堀場製作所社製LA-950V2型粒子径分布測定装置を用いて測定できる。
Tg;アセトン可溶分のガラス転移温度(℃)
a;凝固物に含有されるアルカリ金属およびアルカリ土類金属の価数
が好ましくは100以下であり、より好ましくは90以下であり、さらに好ましくは80以下である。式(1A)で表されるパラメータが小さいほど、凝固物から得られるフィルムの耐温水若しくは耐沸水白化性が向上する傾向がある。
アセトン可溶分とアセトン不溶分は、以下のように測定することができる。すなわち、凝固物2gをアセトン50mLに入れ常温にて24時間撹拌し、得られた液全量を、遠心分離機を用いて、回転数20000rpm、温度0℃、180分間の条件にて、遠心分離して上澄み液と沈殿物を分け採り、それぞれを50℃にて8時間真空下で乾燥させて、アセトン可溶分(上澄み液からアセトンを蒸発させた残渣)およびアセトン不溶分(沈殿物)を得、これらの質量を測定することにより、アセトン可溶分とアセトン不溶分を測定することができる。
。ラテックスの凝固は、公知の方法で行うことができる。凝固法としては、凍結凝固法、塩析凝固法、酸析凝固法などを挙げることができる。これらのうち、高品質な凝固物を連続的に生産することのできる塩析凝固法が好ましい。
第一凝固(凝集工程)は、緩凝集を行う反応であり、乳化ラテックスおよび凝固剤溶液を加熱した状態で混合させ、緩やかな速度で凝集を進行させるものである。
第二凝固(造粒工程)は、第一凝固(凝集工程)で得られたスラリーをさらに加熱することで、凝集しきらない微粒子を減らしかつ、凝固物の嵩密度を高くするものである。
多層構造アクリル系重合体のラテックスまたはアクリル系重合体凝固物の脱水前のスラリーを採取して、堀場製作所社製レーザー回折/散乱式粒子径分布測定装置LA-910を用い、光散乱法によりその平均粒子径を求めた。
ASTM-D1238に準じて、230℃、3.8kg荷重でのメルトフローレート(以下「MFR」と表記する。)を測定した。
JIS K7121に準拠して、示差走査熱量測定装置(島津製作所製、DSC-50)を用いて、250℃まで一度昇温し、次いで室温まで冷却し、次いで室温から230℃までを20℃/分で昇温させる条件にてDSC曲線を測定した。このDSC曲線から求められる中間点ガラス転移温度を本発明におけるガラス転移温度(以下、「Tg」と表記する。)とした。
堀場製作所社製LA-950V2型粒子径分布測定装置を用い、造粒スラリー中の凝固物のメジアン径および75μm以下の粒子比率を体積基準で求めた。
被測定物を105℃に設定された熱風乾燥機内で3時間加熱し、加熱前後での重量変化を測定し、次式により含水率を求めた。
W=〔(Wa-Wb)/Wa〕×100
W;含水率(%)、Wa;乾燥前のサンプル重量(g)、Wb;乾燥後のサンプル重量(g)
1回目の洗浄における遠心分離後の排水の濁度を、JIS K0101に準じ、透過光濁度法により測定を行った。
秤量した約5gの凝固物粉体を圧密せずに乾いた 10mLメスシリンダーに静かに入れる。粉体層の上面を圧密せずに注意深くならし,ゆるみ嵩体積(V)を最小目盛単位まで読み取る。m/Vによって嵩密度(g/cm3)を計算した。
試験試料2gをアセトン50mLに入れ常温にて24時間撹拌した。得られた液全量を、遠心分離機(日立工機(株)製、CR20GIII)を用いて、回転数20000rpm、温度0℃、180分間の条件にて、遠心分離した。上澄み液と沈殿物を分け採り、それぞれを50℃にて8時間真空下で乾燥させて、アセトン可溶分およびアセトン不溶分を得た。
アセトン可溶分またはアセトン不溶分を1g精秤し、クロロホルム50mLで溶解させた。5分間の窒素置換を行った。その後、ブロモチモールブルーを数滴添加した。N/100 KOHエタノール溶液を用いて中和滴定を行った。
対照試料ブランクとして、5分間の窒素置換を行ったクロロホルム50mLについて上記同様に中和滴定を行った。次式により酸価C(mmol/g)を算出した。
C=(A-B)×0.01×F
A=;試験試料における滴定数量(mL)、B=;対照試料におけるブランクの滴定数量(mL)、F=;N/100 KOHエタノール溶液のファクター
秤量した約5gの凝固物粉体を加熱分解し、残渣をICP発光分光分析装置(Varian/SII社製VISTA-PRO型)により測定した。
アクリル系重合体凝固物を190℃、100kg/cm2の条件で熱プレスし厚み200μmの樹脂フィルムを作製する。樹脂フィルムから50mm×50mmの試験片を切り出した。室温下でヘイズ(H0)をJIS K7136に準拠して、ヘイズメータ(村上色彩研究所製、HM-150)を用いて測定した。
次いで、試験片を80℃の水に1時間浸漬した。その後、フィルム表面に付着した水滴を取り除き、フィルムが室温になった状態で、ヘイズを測定した。
室温におけるヘイズから温水浸漬後におけるヘイズへの増加量(ΔH80)を算出した。
耐温水白化性(80℃)で用いた上記樹脂フィルムから50mm×50mmの試験片を切り出した。室温下でヘイズ(H0)をJIS K7136に準拠して、ヘイズメータ(村上色彩研究所製、HM-150)を用いて測定した。
次いで、試験片を100℃の水に4時間浸漬した。その後、フィルム表面に付着した水滴を取り除き、100℃に設定された熱風乾燥機内で8時間乾燥させた。フィルムが室温になった状態で、ヘイズを測定した。
室温におけるヘイズから沸水浸漬後におけるヘイズへの増加量(ΔH100)を算出した。
撹拌機、温度計、窒素ガス導入部、単量体導入管および還流冷却器を具える反応容器内に、イオン交換水150部、DBSS1.3部および炭酸ナトリウム0.05部を仕込み、容器内を窒素ガスで充分に置換して実質的に酸素の影響がない状態とした。その後、反応容器内の温度を80℃にした。反応容器内に過硫酸カリウム0.015部を投入し、5分間撹拌した。次いで、MMA4部、nBA4部およびALMA0.02部からなる単量体混合物を20分間かけて連続的に滴加し、乳化重合を行った。滴加終了後、さらに30分間撹拌し、乳化重合を転化率98%以上となるように行って、硬質重合体(a)を含有するラテックスを得た。
PMMAラテックス[1]を、以下の条件で凝固した。硫酸マグネシウム0.43部、イオン交換水167部の比率である水溶液を80℃に昇温し、上記ラテックスを8.3部/分で撹拌下で12分間フィードした。フィード完了後、液温80℃を保ったまま、1時間撹拌を継続し、凝集スラリーを得た。更に、このスラリーに水を267部加えてから、90℃ に昇温し1時間加熱処理し造粒スラリーを得た。得られた造粒スラリーをスクリューデカンタ式遠心分離機を用いて2100Gの遠心力によりスラリーの洗浄および脱水を行った。続いてスラリー濃度10質量%になるようにイオン交換水を加え、再度スクリューデカンタ式遠心分離機で洗浄および脱水を行い、この作業を計3回繰り返した。得られた含水凝固物の含水率は37質量%であり、メジアン径は135μm、粒子径75μm以下の粒子比率は22%であった。
使用するPMMAラテックスの種類と量、水の量、凝固剤の種類と量、凝固の時間、温度、洗浄・脱水回数を表2および表3に記載のとおりに変更した以外は実施例1と同じ方法でアクリル系重合体凝固物を得た。なお、表3において、比較例2は排水濁度が1040、脱水後樹脂含水率が54質量%と高く、品質の劣る凝固物が得られたので、樹脂物性、含有金属量、耐温水白化性の試験は行わなかった。
ラテックス[1]を-20℃の雰囲気に4時間置いて凍結させた。硫酸マグネシウムを成分とする若干量の消泡剤を添加した3倍量の80℃の水に、得られた凍結物を投入して融解させて、スラリーを得た。スクリューデカンタ式遠心分離機を用いて2100Gの遠心力によりスラリーの洗浄および脱水を行った。続いてスラリー濃度10%になるようにイオン交換水を加え、再度スクリューデカンタ式遠心分離機で洗浄および脱水を行った。
Claims (8)
- 塩析凝固法により得られる請求項1に記載の凝固物。
- 多層構造アクリル系重合体がアセトン可溶分およびアセトン不溶分からなり、アセトン可溶分が、メチルメタクリレートに由来する構造単位80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~20質量%を含み、80~100℃のガラス転移温度を有し、アセトン不溶分がメチルメタクリレートに由来する構造単位20~60質量%、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位40~80質量%を含み、0℃以下のガラス転移温度を有する、請求項1または2に記載の凝固物。
- 多層構造アクリル系重合体がアセトン可溶分およびアセトン不溶分からなり、アセトン可溶分が、メチルメタクリレートに由来する構造単位80~99質量%、およびアルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位1~20質量%を含み、90~110℃のガラス転移温度を有し、アセトン不溶分がメチルメタクリレートに由来する構造単位40~60質量%、アルキル基の炭素数が1~8であるアルキルアクリレートに由来する構造単位40~60質量%、およびそれと共重合可能なビニル系単量体0~20質量%を含み、0℃以下のガラス転移温度を有する請求項1または2に記載の凝固物。
- 請求項1~4に記載のいずれかの凝固物を用いて得られる成形体。
- 請求項1~4に記載のいずれかの凝固物を用いて得られるフィルム。
- 請求項1~4に記載のいずれかの凝固物を用いて得られるフィルムからなる少なくとも1つの層と、他の熱可塑性重合体成形品からなる少なくとも1つの層とを有する積層体。
- 以下の工程1~5
工程1:乳化剤の存在下にアクリル系単量体、共重合可能な他の単量体、グラフト化剤および/または架橋剤を重合してラテックス(I)を得る工程、
工程2:ラテックス(I)の存在下にアクリル系単量体、共重合可能な他の単量体、グラフト化剤、任意成分としての架橋剤を重合してラテックス(II)を得る工程、
工程3:ラテックス(II)の存在下にアクリル系単量体を重合してラテックス(III)を得る工程、
工程4:ラテックス(III)を凝固剤の存在下に緩凝集して、多層構造アクリル系重合体の凝集体を得る工程、
工程5:工程4で得られた多層構造アクリル系重合体の凝集体を加熱して、多層構造アクリル系重合体の凝固物を得る工程
を含む、嵩密度が0.3~0.6g/cm3、メジアン径が50~400μm、粒子径75μm以下の粒子の比率が50%以下で、かつ含有するアルカリ金属およびアルカリ土類金属が下記式(1)を満たすことを特徴とする多層構造アクリル系重合体凝固物の製造方法。
Tg;アセトン可溶分のガラス転移温度(℃)
a;凝固物に含有されるアルカリ金属およびアルカリ土類金属の価数。
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