JPH058922B2 - - Google Patents
Info
- Publication number
- JPH058922B2 JPH058922B2 JP62211163A JP21116387A JPH058922B2 JP H058922 B2 JPH058922 B2 JP H058922B2 JP 62211163 A JP62211163 A JP 62211163A JP 21116387 A JP21116387 A JP 21116387A JP H058922 B2 JPH058922 B2 JP H058922B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- graft copolymer
- cab
- parts
- copolymer resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 47
- 239000000178 monomer Substances 0.000 claims description 35
- 229920000578 graft copolymer Polymers 0.000 claims description 32
- 150000008065 acid anhydrides Chemical class 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 125000004063 butyryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 26
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- 239000008096 xylene Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 11
- 229920002554 vinyl polymer Polymers 0.000 description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000000020 Nitrocellulose Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 229920001220 nitrocellulos Polymers 0.000 description 4
- 239000003505 polymerization initiator Substances 0.000 description 4
- 239000000126 substance Substances 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
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-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
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- -1 Acetate ester Chemical class 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- CWZPGMMKDANPKU-UHFFFAOYSA-L butyl-di(dodecanoyloxy)tin Chemical compound CCCC[Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O CWZPGMMKDANPKU-UHFFFAOYSA-L 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
〔産業上の利用分野〕
本発明はグラフト共重合体樹脂の製造方法に関
し、さらに詳しくは、乾燥性、相溶性、ならびに
溶解性を向上させたセルロースアセテートブチレ
ートと重合性単量体のグラフト共重合体樹脂の製
造方法に関するものである。
〔従来の技術〕
セルロースアセテートブチレート（以下、
CABと称する）にビニル系単量体を共重合させ
て得られるグラフト共重合体樹脂は、乾燥性、硬
度等に優れているため、最近、塗料業界、特に自
動車補修用塗料樹脂として注目されている。
このようなグラフト共重合体樹脂の合成方法と
しては、次のような方法が提案されている。
CABの水素を引き抜き易い有機過酸化物を
重合開始剤に用い、CABにビニル系単量体を
直接共重合させる方法（例えば特開昭49−
115126号、同55−133472号、同56−157463号、
同56−163159号等）。
CABのヒドロキシル基に対し、不飽和結合
またはラジカルにより水素を引き抜かれうる炭
素−水素結合を有する酸無水物あるいはイソシ
アネート等を導入した後、ビニル系単量体を共
重合させる方法（例えば特開昭48−80192号、
同50−48030号、同50−48031号、同50−48032
号等）。
CABのアセテート、ブチレートのエステル
部位にマレイン酸エステルあるいはフマル酸エ
ステルなどの共重合可能な不飽和結合を導入し
た後にビニル系単量体を共重合させる方法（例
えば特開昭60−58415号、同60−110712号等）。
〔発明が解決しようとする問題点〕
しかし、これらの製造方法においては、グラフ
ト化率が極めて低いか、あるいは最終的にゲル化
することなくグラフト共重合体樹脂を得るために
は煩雑な製造工程を必要とする。
例えばのCABの水素を引き抜き易い有機過
酸化物を重合開始剤に用いて、CABにビニル系
単量体を直接共重合させる方法では、グラフト化
が不充分なため、本来鮮映性および光沢を与える
特性をもつスチレンまたはその誘導体を任意の割
合で使用することができず、得られたグラフト共
重合体樹脂溶液に白濁を生じ、かつこれにより造
膜したフイルムも白濁を生ずる。
またのCABのヒドロキシル基に対し、不飽
和結合またはラジカルにより水素を引き抜かれう
る炭素−水素結合を有する酸無水物あるいはイソ
シアネート等を導入した後ビニル系単量体を共重
合させる方法、もしくはのCABのアセテート、
ブチレートのエステル部位にマレイン酸エステル
あるいはフマル酸エステルなどの共重合可能な不
飽和結合を導入した後にビニル系単量体を共重合
させる方法では、鮮映性および光沢を与える特性
をもつスチレンまたはその誘導体を任意の割合で
使用することができるものの、グラフト共重合体
樹脂を得るに際しては、予めCABに共重合可能
な不飽和結合または炭素−水素結合が多く導入さ
れている、いわゆるCABマクロマーを用いるた
め、CABマクロマー溶液中に、ビニル系単量体
を滴下した場合、合成中にゲル化を生ずる。この
ため予めCABマクロマーを製造した後に、CAB
マクロマーを取り出し、CABマクロマーをビニ
ル系単量体中に配合して滴下重合させる必要があ
り、非常に煩雑な製造工程を必要とするなどの問
題点がある。
本発明はこれらの問題点を解決するためのもの
で、ゲル化を生ずることなく、充分なグラフト化
が可能で、硬度、乾燥性および溶剤に対する溶解
性に優れ、かつスチレン等の他の樹脂との相溶性
に優れたグラフト共重合体樹脂の製造方法を提供
することを目的としている。
〔問題点を解決するための手段〕
本発明は、
(A)：セルロースアセテートブチレート２〜60重量
％、
(B)：無水コハク酸、無水フタル酸、無水トリメリ
ツト酸および無水ピロメリツト酸から選ばれる
１種以上の重合性不飽和結合を含まない酸無水
物（以下単に、不飽和結合を含まない酸無水物
という）0.05〜15重量％、
(C)：ヒドロキシル基含有重合性単量体0.1〜70重
量％、および
(D)：グリシジル基を含まないその他の共重合可能
な重合性単量体97.85〜25重量％
を反応させることを特徴とするグラフト共重合体
樹脂の製造方法である。
本発明において使用される(A)のCABとしては、
市販のCABがいずれも使用可能であるが、アセ
チル基1.8〜15重量％、ブチリル基36〜58重量％、
ヒドロキシル基５重量％以下を含有するCABが
好適に使用できる。
このようなCABは(A)，(B)，(C)，(D)の合計量に
対して２〜60重量％使用される。CABが２重量
％未満の場合に得られるグラフト共重合体樹脂は
クリヤーな塗膜が得られるが、乾燥性、硬度が不
充分である。またCABが60重量％を越える場合
は、得られるグラフト共重合体樹脂の樹脂固形分
が著しく低下し、塗料の実用上好ましくない。
(B)の不飽和結合を含まない酸無水物としては、
無水コハク酸、無水フタル酸、無水トリメリツト
酸、無水ピロメリツト酸等が使用できる。このよ
うな不飽和結合を含まない酸無水物は(A)，(B)，
(C)，(D)の合計量に対して0.05〜15重量％使用され
る。不飽和結合を含まない酸無水物が0.05重量％
未満では、CABのグラフト化が不充分となり、
得られるグラフト共重合体樹脂の溶解性が不充分
となる。また不飽和結合を含まない酸無水物が15
重量％を越えると、未反応の不飽和結合を含まな
い酸無水物が得られたグラフト共重合体樹脂溶液
中に残存し、塗膜性能を低下させ好ましくない。
(C)のヒドロキシル基含有重合性単量体として
は、２−ヒドロキシエチルアクリレート、２−ヒ
ドロキシエチルメタクリレート、２−ヒドロキシ
プロピルアクリレート、２−ヒドロキシプロピル
メタクリレート等が使用できる。このようなヒド
ロキシル基含有重合性単量体は(A)，(B)，(C)，(D)の
合計量に対して0.1〜70重量％使用される。ヒド
ロキシル基含有重合性単量体が0.1重量％未満で
は、CABのグラフト化が不充分となり、得られ
たグラフト共重合体樹脂の溶解性が不充分とな
る。ヒドロキシル基含有重合性単量体が70重量％
を越えると、得られるグラフト共重合体樹脂の溶
解性が不充分となり、また架橋剤を使用する場
合、架橋点が多くなりすぎて塗膜を脆くさせるの
で好ましくない。
さらに本発明に使用される(D)のグリシジル基を
含まないその他の共重合可能な重合性単量体とし
ては、公知のα，β−エチレン性不飽和基を有す
るグリシジル基を含まない任意のビニル系単量体
が好適に使用され、具体的には下記のものが挙げ
られる。
(1) ビニル単量体：例えばスチレン、ビニルトル
エン、α−メチルスチレン、酢酸ビニル、アク
リロニトリル、メタクリロニトリル等。
(2) アクリル酸あるいはメタクリル酸のアルキル
またはシクロアルキルエステル：例えばメチル
アクリレート、メチルメタクリレート、エチル
アクリレート、エチルメタクリレート、ｎ−ブ
チルアクリレート、ｎ−ブチルメタクリレー
ト、ｉ−ブチルアクリレート、ｉ−ブチルメタ
クリレート、ｔ−ブチルアクリレート、ｔ−ブ
チルメタクリレート、シクロヘキシルアクリレ
ート、シクロヘキシルメタクリレート、２−エ
チルエキシルアクリレート、２−エチルヘキシ
ルメタクリレート、ラウリルアクリレート、ラ
ウリルメタクリレート、ステアリルアクリレー
ト、ステアリルメタクリレート等。
(3) α，β−エチレン性不飽和カルボン酸：例え
ばアクリル酸、メタクリル酸、イタコン酸等。
(4) アクリルアミドあるいはメタクリルアミド
類：例えばアクリルアミド、メタクリルアミ
ド、Ｎ−メチルアクリルアミド、Ｎ−メチルメ
タクリルアミド、Ｎ−メチロールメタクリルア
ミド、Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ，
Ｎ−ジメチルメタクリルアミド等。
これらの重合性単量体は、(A)，(B)，(C)，(D)の合
計量に対して97.85〜25重量％使用される。
本発明のグラフト共重合体樹脂を製造するに
は、反応触媒として、マンガン、鉛、コバルト、
亜鉛、スズ、ニツケル等のナフテン酸もしくはオ
クチル酸塩や、ジブチルスズラウレート、塩化ス
ズ、酸化鉄等の金属化合物などの公知の触媒を単
独もしくは複数用いて、重合開始剤および溶剤の
存在下、室温から200℃の温度で、上記(A)，(B)，
(C)，(D)を反応させることにより、グラフト共重合
体樹脂が得られる。
このとき(B)の不飽和結合を含まない酸無水物と
(C)のヒドロキシル基含有重合性単量体との開環反
応により得られるカルボキシル基含有重合性単量
体、あるいはこの重合性単量体と(D)のグリシジル
基を含まないその他の重合性単量体との共重合に
より得られるポリマー中のカルボキシル基と、(A)
のCABのアセテートあるいはブチレートのエス
テル部位とのエステル交換反応によりCABがグ
ラフト共重合される。
上記共重合反応に使用される重合開始剤として
は、例えば過酸化ベンゾイル、過酸化ラウロイ
ル、ジクミルペルオキシド、ｔ−ブチルヒドロペ
ルオキシド、クメンヒドロペルオキシド、ｔ−ブ
チルペルオキシベンゾエート、ｔ−ブチルペルオ
キシオクトエート等の有機過酸化物、アゾビスイ
ソブチロニトリル、アゾビスジメチルバレロニト
リル等のアゾ化合物などのラジカル重合開始剤が
好適である。
また合成溶剤としては、例えばベンゼン、トル
エン、キシレン等のアルキルベンゼン、酢酸エチ
ル、酢酸ブチル、酢酸イソブチル等の酢酸エステ
ル、アセトン、メチルイソブチルケトン等のケト
ンなどが単独もしくは任意の割合で併用される。
本発明の製造方法により得られるグラフト共重
合体樹脂によつて形成されるクリヤー塗膜の硬度
および乾燥性と、得られたグラフト共重合体樹脂
と同様な重合性単量体組成により得られるポリマ
ーおよびCABの混合樹脂によつて形成されるク
リヤー塗膜の硬度および乾燥性とを比較すると、
前者の方が優れている。
またベンゼン、トルエン、キシレン等の芳香族
炭化水素への溶解性についても、グラフト共重合
体樹脂の方が著しく優れている。グラフト共重合
体樹脂と同様な重合性単量体組成により得られる
ポリマーとCABとの混合樹脂は、グラフト共重
合体樹脂溶液と同程度のクリヤー状態を得ようと
すれば、CABに対し良溶剤となる酢酸エステル、
ケトンなどの溶剤を、グラフト共重合体樹脂の場
合よりも多量に用いる必要がある。これはCAB
がグラフト化合物されることにより、ベンゼン、
トルエン、キシレン等の芳香族炭化水素への溶解
性が著しく改善され、酢酸エステル、ケトンなど
の溶剤を多量に用いる必要がなくなることを示
す。
さらに上記製造方法により得られるグラフト共
重合体樹脂においては、スチレンまたはその誘導
体を任意の割合で使用することができるので、得
られたグラフト共重合体樹脂は、ニトロセルロー
スに対しても良好な相溶性を有している。このた
めCABを用いながらも、本来併用が著しく困難
なニトロセルロースとの併用も可能となる。
CABは高スチレン含有樹脂との相溶性が不良で
あるが、本発明によりグラフト共重合体樹脂とす
ることにより、高スチレン含有樹脂との相溶性が
著しく向上し、CABを用いながらも、スチレン
またはその誘導体の特長である鮮映性および光沢
を損なうことがない。
〔発明の効果〕
以上説明したように、本発明によれば、CAB
に不飽和結合を含まない特定の酸無水物、ヒドロ
キシル基含有重合性単量体、およびグリシジル基
を含まないその他の共重合可能な重合性単量体を
反応させてグラフト共重合体樹脂を製造するた
め、ゲル化することなく、CABへのグラフト化
効率も高く、CABの特長である硬度、乾燥性等
を損なうことなく、グラフト化により、ベンゼ
ン、トルエン、キシレン等の芳香族炭化水素への
溶解性にも優れ、またアクリル、高スチレン含有
樹脂およびニトロセルロース等の他の樹脂との相
溶性も良好なグラフト共重合体樹脂を製造するこ
とができる。
〔実施例〕
以下、実施例および比較例により本発明をさら
に詳細に説明する。各例中、部および％は特に注
釈がない限り重量部および重量％を示す。
実施例 １
温度計、攪拌機、還流冷却管、およびモノマー
滴下装置を備えた反応器に、キシレン34部、セル
ロースアセテートブチレート「CAB−551−0.2」
（イ−ストマンケミカルプロダクト社製、商品名）
3.5部、無水フタル酸0.4部、ジブチルスズラウレ
ート0.1部を仕込み、徐々に昇温しながらセルロ
ースアセテートブチレートを溶解させ、キシレン
還流温度（約140℃）まで加熱する。還流温度に
２時間保ち、滴下装置よりスチレン18.4部、メチ
ルメタクリレート5.2部、ブチルメタクリレート
2.7部、ラウリルメタクリレート11.5部、２−ヒ
ドロキシエチルメタクリレート7.2部、アクリル
酸0.5部およびｔ−ブチルペルオキシベンゾエー
ト（パーブチルＺ、日本油脂(株)製、登録商標）
0.45部の混合液を３時間かけて滴下した。滴下終
了後３時間還流温度に保ち、次いでｔ−ブチルペ
ルオキシベンゾエート0.05部およびキシレン１部
を滴下装置より滴下した。さらに２時間還流温度
に保ち反応を続けた後、酢酸ブチル15部を加え室
温まで冷却して、加熱残分50.2％、25℃でのあわ
粘度Z1の均一で透明な樹脂溶液を得た。
実施例 ２〜12
実施例１と同様の反応装置を用い、同様の反応
操作を行い、表１の仕込組成により、表１の特性
値の樹脂溶液を得た。
比較例 １
実施例１と同様の反応装置にキシレン34部、セ
ルロースアセテートブチレート「CAB−551−
0.2」（イ−ストマンケミカルプロダクト社製）
3.5部を仕込み、徐々に昇温しながらセルロース
アセテートブチレートを溶解させ、キシレン還流
温度（約140℃）まで加熱する。還流温度に２時
間保ち、滴下装置よりスチレン15.5部、メチルメ
タクリレート5.2部、ブチルメタクリレート6.1
部、ラウリルメタクリレート11.5部、２−ヒドロ
キシエチルメタクリレート7.2部、アクリル酸0.5
部およびｔ−ブチルペルオキシベンゾエート0.45
部の混合液を３時間かけて滴下した。滴下終了後
３時間還流温度に保ち、次いでｔ−ブチルペルオ
キシベンゾエート0.05部およびキシレン１部を滴
下し、さらに２時間還流温度に保ち反応を続けた
後、酢酸ブチル15部を加え室温まで冷却した。得
られた樹脂溶液は流動性に劣る白濁したものであ
つた。
比較例 ２
実施例１と同様の反応装置にキシレン34部、セ
ルロースアセテートブチレート「CAB−551−
0.2」（イ−ストマンケミカルプロダクト社製）
3.5部、無水フタル酸0.4部、ブチルスズジラウレ
ート0.1部を仕込み、徐々に昇温しながらセルロ
ースアセテートブチレートを溶解させ、キシレン
還流温度（約140℃）まで加熱する。還流温度に
２時間保ち、滴下装置よりスチレン20.0部、メチ
ルメタクリレート5.2部、ブチルメタクリレート
8.8部、ラウリルメタクリレート11.5部およびｔ
−ブチルペルオキシベンゾエート0.45部の混合液
を３時間かけて滴下した。滴下終了後３時間還流
温度に保ち、次いでｔ−ブチルペルオキシベンゾ
エート0.05部およびキシレン１部を滴下し、さら
に２時間還流温度に保ち反応を続けた後、酢酸ブ
チル15部を加え室温まで冷却した。得られた樹脂
溶液は流動性に劣る白濁したものであつた。
比較例 ３
実施例１と同様の反応装置にキシレン34部、セ
ルロースアセテートブチレート「CAB−551−
0.2」（イ−ストマンケミカルプロダクト社製）
3.5部、無水マレイン酸0.4部、ジブチルスズジラ
ウレート0.1部を仕込み、徐々に昇温しながらセ
ルロースアセテートブチレートを溶解させ、キシ
レン還流温度（約140℃）まで加熱する。還流温
度に２時間保ち、滴下装置よりスチレン18.4部、
メチルメタクリレート5.2部、ブチルメタクリレ
ート2.7部、ラウリルメタクリレート11.5部、２
−ヒドロキシエチルメタクリレート7.2部、アク
リル酸0.5部およびｔ−ブチルペルオキシベンゾ
エート0.45部の混合液を３時間かけて滴下した。
滴下終了後、溶液粘度が著しく上昇しゲル化し
た。
次に各実施例ならびに比較例で得た各樹脂の特
性ならびに塗膜性能を表２に示す。
[Industrial Field of Application] The present invention relates to a method for producing a graft copolymer resin, and more specifically, to a method for producing a graft copolymer resin, and more specifically, a method for producing a graft copolymer resin of cellulose acetate butyrate and a polymerizable monomer, which has improved drying properties, compatibility, and solubility. The present invention relates to a method for producing a polymer resin. [Prior art] Cellulose acetate butyrate (hereinafter referred to as
Graft copolymer resin obtained by copolymerizing vinyl monomer with CAB) has recently attracted attention in the paint industry, especially as a paint resin for automobile refinishing, due to its excellent drying properties and hardness. There is. The following methods have been proposed as methods for synthesizing such graft copolymer resins. A method in which a vinyl monomer is directly copolymerized with CAB using an organic peroxide that easily extracts hydrogen from CAB as a polymerization initiator (for example,
No. 115126, No. 55-133472, No. 56-157463,
No. 56-163159, etc.). A method of copolymerizing vinyl monomers after introducing an acid anhydride or isocyanate having a carbon-hydrogen bond from which hydrogen can be extracted by an unsaturated bond or radical into the hydroxyl group of CAB (for example, JP-A-Show) No. 48-80192,
No. 50-48030, No. 50-48031, No. 50-48032
No. etc.). A method in which a copolymerizable unsaturated bond such as maleate or fumarate is introduced into the acetate or butyrate ester part of CAB, and then a vinyl monomer is copolymerized (for example, JP-A-60-58415, 60-110712, etc.). [Problems to be Solved by the Invention] However, in these production methods, the grafting rate is extremely low, or a complicated production process is required to obtain the graft copolymer resin without gelation. Requires. For example, in the method of directly copolymerizing vinyl monomers with CAB using an organic peroxide that easily abstracts hydrogen from CAB as a polymerization initiator, grafting is insufficient, so the original image clarity and gloss are Styrene or its derivatives having the properties given above cannot be used in any proportion, and the obtained graft copolymer resin solution becomes cloudy, and the resulting film also becomes cloudy. In addition, a method in which an acid anhydride or isocyanate having a carbon-hydrogen bond from which hydrogen can be extracted by an unsaturated bond or a radical is introduced into the hydroxyl group of CAB, and then a vinyl monomer is copolymerized, or CAB acetate,
In the method of introducing a copolymerizable unsaturated bond such as maleate or fumarate into the ester moiety of butyrate and then copolymerizing it with a vinyl monomer, styrene, which has the properties of providing sharpness and gloss, or Although derivatives can be used in any ratio, when obtaining a graft copolymer resin, a so-called CAB macromer, in which many copolymerizable unsaturated bonds or carbon-hydrogen bonds are introduced into CAB, is used. Therefore, when a vinyl monomer is dropped into a CAB macromer solution, gelation occurs during synthesis. For this reason, after producing CAB macromer in advance, CAB
It is necessary to take out the macromer, blend the CAB macromer into the vinyl monomer, and perform drop polymerization, which poses problems such as the need for a very complicated manufacturing process. The present invention is intended to solve these problems, and is capable of sufficient grafting without causing gelation, has excellent hardness, drying properties, and solubility in solvents, and is compatible with other resins such as styrene. It is an object of the present invention to provide a method for producing a graft copolymer resin having excellent compatibility. [Means for Solving the Problems] The present invention provides: (A): 2 to 60% by weight of cellulose acetate butyrate; (B): selected from succinic anhydride, phthalic anhydride, trimellitic anhydride and pyromellitic anhydride. 0.05 to 15% by weight of acid anhydride that does not contain one or more types of polymerizable unsaturated bonds (hereinafter simply referred to as acid anhydride that does not contain unsaturated bonds), (C): 0.1 to 15% of hydroxyl group-containing polymerizable monomer 70% by weight, and (D): 97.85 to 25% by weight of another copolymerizable monomer not containing a glycidyl group. The CAB (A) used in the present invention is:
Any commercially available CAB can be used, including 1.8 to 15% by weight of acetyl groups, 36 to 58% by weight of butyryl groups,
CAB containing 5% by weight or less of hydroxyl groups can be preferably used. Such CAB is used in an amount of 2 to 60% by weight based on the total amount of (A), (B), (C), and (D). The graft copolymer resin obtained when the CAB content is less than 2% by weight provides a clear coating film, but has insufficient drying properties and hardness. Furthermore, if the CAB content exceeds 60% by weight, the resin solid content of the resulting graft copolymer resin will be significantly reduced, which is undesirable for practical use as a coating material. As acid anhydrides (B) that do not contain unsaturated bonds,
Succinic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. can be used. Acid anhydrides that do not contain such unsaturated bonds are (A), (B),
It is used in an amount of 0.05 to 15% by weight based on the total amount of (C) and (D). 0.05% by weight of acid anhydride without unsaturated bonds
If the amount is less than
The resulting graft copolymer resin has insufficient solubility. In addition, acid anhydrides that do not contain unsaturated bonds are 15
If it exceeds % by weight, the acid anhydride containing no unreacted unsaturated bonds remains in the obtained graft copolymer resin solution, which is undesirable because it deteriorates the coating film performance. As the hydroxyl group-containing polymerizable monomer (C), 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. can be used. Such a hydroxyl group-containing polymerizable monomer is used in an amount of 0.1 to 70% by weight based on the total amount of (A), (B), (C), and (D). If the amount of the hydroxyl group-containing polymerizable monomer is less than 0.1% by weight, the grafting of CAB will be insufficient, and the resulting graft copolymer resin will have insufficient solubility. 70% by weight of hydroxyl group-containing polymerizable monomer
If it exceeds this amount, the resulting graft copolymer resin will have insufficient solubility, and if a crosslinking agent is used, there will be too many crosslinking points, making the coating film brittle, which is not preferred. Further, as the other copolymerizable monomer (D) which does not contain a glycidyl group and is used in the present invention, any known copolymerizable monomer which does not contain a glycidyl group and has an α,β-ethylenically unsaturated group can be used. Vinyl monomers are preferably used, and specific examples include the following. (1) Vinyl monomers: for example, styrene, vinyltoluene, α-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile, etc. (2) Alkyl or cycloalkyl esters of acrylic acid or methacrylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, t- Butyl acrylate, t-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-ethylexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, etc. (3) α,β-ethylenically unsaturated carboxylic acids: for example, acrylic acid, methacrylic acid, itaconic acid, etc. (4) Acrylamide or methacrylamide: for example, acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N-methylolmethacrylamide, N,N-dimethylacrylamide, N,
N-dimethylmethacrylamide etc. These polymerizable monomers are used in an amount of 97.85 to 25% by weight based on the total amount of (A), (B), (C), and (D). In order to produce the graft copolymer resin of the present invention, manganese, lead, cobalt,
A known catalyst such as naphthenic acid or octylate such as zinc, tin, or nickel, or a metal compound such as dibutyltin laurate, tin chloride, or iron oxide is used alone or in combination at room temperature in the presence of a polymerization initiator and a solvent. At a temperature of 200℃, the above (A), (B),
A graft copolymer resin is obtained by reacting (C) and (D). In this case, the acid anhydride (B) that does not contain unsaturated bonds and
A carboxyl group-containing polymerizable monomer obtained by a ring-opening reaction with the hydroxyl group-containing polymerizable monomer (C), or other polymerizable monomers that do not contain a glycidyl group and this polymerizable monomer and (D). Carboxyl groups in the polymer obtained by copolymerization with monomers and (A)
CAB is graft copolymerized by a transesterification reaction with an acetate or butyrate ester moiety of CAB. Examples of the polymerization initiator used in the above copolymerization reaction include benzoyl peroxide, lauroyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxybenzoate, t-butyl peroxyoctoate, etc. Radical polymerization initiators such as organic peroxides, azo compounds such as azobisisobutyronitrile, and azobisdimethylvaleronitrile are suitable. As the synthesis solvent, for example, alkylbenzenes such as benzene, toluene, and xylene, acetate esters such as ethyl acetate, butyl acetate, and isobutyl acetate, and ketones such as acetone and methyl isobutyl ketone are used alone or in combination in any proportion. The hardness and drying properties of the clear coating film formed from the graft copolymer resin obtained by the production method of the present invention, and the polymer obtained from the same polymerizable monomer composition as the obtained graft copolymer resin. Comparing the hardness and drying properties of the clear coating film formed by the mixed resin of CAB and CAB,
The former is better. Graft copolymer resins are also significantly superior in solubility in aromatic hydrocarbons such as benzene, toluene, and xylene. A mixed resin of CAB and a polymer obtained with the same polymerizable monomer composition as the graft copolymer resin is a good solvent for CAB if you want to obtain the same clear state as the graft copolymer resin solution. Acetate ester,
Solvents such as ketones need to be used in higher amounts than with graft copolymer resins. This is CAB
By grafting compound, benzene,
This shows that the solubility in aromatic hydrocarbons such as toluene and xylene is significantly improved, and there is no need to use large amounts of solvents such as acetate and ketones. Furthermore, in the graft copolymer resin obtained by the above production method, styrene or its derivatives can be used in any proportion, so the obtained graft copolymer resin has good compatibility with nitrocellulose. It has solubility. Therefore, while using CAB, it is also possible to use it in combination with nitrocellulose, which is originally extremely difficult to use in combination.
CAB has poor compatibility with high styrene-containing resins, but by making it into a graft copolymer resin according to the present invention, the compatibility with high styrene-containing resins is significantly improved. It does not impair the image clarity and gloss, which are the characteristics of derivatives. [Effects of the Invention] As explained above, according to the present invention, CAB
A graft copolymer resin is produced by reacting a specific acid anhydride that does not contain an unsaturated bond, a hydroxyl group-containing polymerizable monomer, and other copolymerizable monomers that do not contain a glycidyl group. Therefore, the grafting efficiency to CAB is high without gelation, and the grafting can be used to graft aromatic hydrocarbons such as benzene, toluene, and xylene without impairing the hardness and drying properties that are the characteristics of CAB. It is possible to produce a graft copolymer resin that has excellent solubility and also good compatibility with other resins such as acrylic, high styrene-containing resins, and nitrocellulose. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples. In each example, parts and percentages are by weight unless otherwise noted. Example 1 34 parts of xylene and cellulose acetate butyrate "CAB-551-0.2" were placed in a reactor equipped with a thermometer, stirrer, reflux condenser, and monomer dropping device.
(Manufactured by Eastman Chemical Products, product name)
Add 3.5 parts of phthalic anhydride, 0.4 parts of phthalic anhydride, and 0.1 part of dibutyltin laurate, gradually raise the temperature to dissolve cellulose acetate butyrate, and heat to the xylene reflux temperature (approximately 140°C). Keep at reflux temperature for 2 hours and add 18.4 parts of styrene, 5.2 parts of methyl methacrylate, and butyl methacrylate from a dropping device.
2.7 parts, lauryl methacrylate 11.5 parts, 2-hydroxyethyl methacrylate 7.2 parts, acrylic acid 0.5 parts and t-butyl peroxybenzoate (Perbutyl Z, manufactured by NOF Corporation, registered trademark)
0.45 parts of the mixture was added dropwise over 3 hours. After the dropwise addition was completed, the temperature was kept at reflux for 3 hours, and then 0.05 part of t-butylperoxybenzoate and 1 part of xylene were added dropwise from a dropping device. After continuing the reaction by keeping the temperature at reflux for another 2 hours, 15 parts of butyl acetate was added and the mixture was cooled to room temperature to obtain a uniform and transparent resin solution with a heating residue of 50.2% and a foam viscosity of Z 1 at 25°C. Examples 2 to 12 Using the same reaction apparatus as in Example 1, the same reaction operations were performed to obtain resin solutions having the characteristic values shown in Table 1 according to the charging composition shown in Table 1. Comparative Example 1 In a reactor similar to Example 1, 34 parts of xylene and cellulose acetate butyrate "CAB-551-
0.2” (manufactured by Eastman Chemical Products)
Charge 3.5 parts, gradually raise the temperature to dissolve cellulose acetate butyrate, and heat to xylene reflux temperature (approximately 140°C). Keep at reflux temperature for 2 hours and add 15.5 parts of styrene, 5.2 parts of methyl methacrylate, and 6.1 parts of butyl methacrylate from a dropping device.
parts, lauryl methacrylate 11.5 parts, 2-hydroxyethyl methacrylate 7.2 parts, acrylic acid 0.5 parts
part and t-butyl peroxybenzoate 0.45
A mixture of 1 part and 1 part was added dropwise over 3 hours. After the dropwise addition was completed, the mixture was kept at reflux temperature for 3 hours, then 0.05 part of t-butyl peroxybenzoate and 1 part of xylene were added dropwise, and the mixture was kept at reflux temperature for another 2 hours to continue the reaction, and then 15 parts of butyl acetate was added and cooled to room temperature. The resulting resin solution was cloudy and had poor fluidity. Comparative Example 2 In a reactor similar to Example 1, 34 parts of xylene and cellulose acetate butyrate "CAB-551-
0.2” (manufactured by Eastman Chemical Products)
Add 3.5 parts of phthalic anhydride, 0.4 parts of phthalic anhydride, and 0.1 part of butyltin dilaurate, gradually raise the temperature to dissolve cellulose acetate butyrate, and heat to the xylene reflux temperature (approximately 140°C). Keep at reflux temperature for 2 hours and add 20.0 parts of styrene, 5.2 parts of methyl methacrylate, and butyl methacrylate from a dropping device.
8.8 parts, lauryl methacrylate 11.5 parts and t
A mixed solution of 0.45 parts of -butyl peroxybenzoate was added dropwise over 3 hours. After the dropwise addition was completed, the mixture was kept at reflux temperature for 3 hours, then 0.05 part of t-butyl peroxybenzoate and 1 part of xylene were added dropwise, and the mixture was kept at reflux temperature for another 2 hours to continue the reaction, and then 15 parts of butyl acetate was added and cooled to room temperature. The resulting resin solution was cloudy and had poor fluidity. Comparative Example 3 In a reactor similar to Example 1, 34 parts of xylene and cellulose acetate butyrate "CAB-551-
0.2” (manufactured by Eastman Chemical Products)
Add 3.5 parts of maleic anhydride, 0.4 parts of maleic anhydride, and 0.1 part of dibutyltin dilaurate, gradually raise the temperature to dissolve cellulose acetate butyrate, and heat to the xylene reflux temperature (approximately 140°C). Keep at reflux temperature for 2 hours, add 18.4 parts of styrene from a dropping device,
Methyl methacrylate 5.2 parts, butyl methacrylate 2.7 parts, lauryl methacrylate 11.5 parts, 2
A mixed solution of 7.2 parts of -hydroxyethyl methacrylate, 0.5 parts of acrylic acid and 0.45 parts of t-butyl peroxybenzoate was added dropwise over 3 hours.
After the dropwise addition was completed, the solution viscosity increased significantly and gelatinized. Next, Table 2 shows the characteristics and coating film performance of each resin obtained in each Example and Comparative Example.
【表】【table】
【表】
(3) 樹脂固形分当り
[Table] (3) Per resin solid content
【表】【table】
【表】
以上の結果から明らかなように、本発明の製造
方法による実施例１〜12のグラフト共重合体樹脂
は乾燥塗膜、トルエン、キシレン等の芳香族炭化
水素への溶解性に優れ、またニトロセルロースや
高スチレン含有樹脂との相溶性にも優れている。
それに対し、不飽和結合を含まない酸無水物
（Ｂ成分）を含まない比較例１、ならびにヒドロ
キシル基含有重合性単量体（Ｃ成分）を含まない
比較例２の樹脂溶液は、グラフト化も不充分で、
乾燥塗膜、溶解性、相溶性も劣つている。また不
飽和結合を有する酸無水物を用いた比較例３は、
合成中にゲル化を生ずる。[Table] As is clear from the above results, the graft copolymer resins of Examples 1 to 12 produced by the production method of the present invention have excellent solubility in dry coatings, aromatic hydrocarbons such as toluene and xylene, It also has excellent compatibility with nitrocellulose and high styrene-containing resins. On the other hand, the resin solutions of Comparative Example 1, which does not contain an acid anhydride (component B) that does not contain unsaturated bonds, and Comparative Example 2, which does not contain a hydroxyl group-containing polymerizable monomer (component C), do not cause grafting. Not enough,
The dry coating film, solubility, and compatibility are also poor. In addition, Comparative Example 3 using an acid anhydride having an unsaturated bond,
Gelation occurs during synthesis.
Claims (1)
重量％、 (B)：無水コハク酸、無水フタル酸、無水トリメリ
ツト酸および無水ピロメリツト酸から選ばれる
１種以上の重合性不飽和結合を含まない酸無水
物0.05〜15重量％ (C)：ヒドロキシル基含有重合性単量体0.1〜70重
量％、および (D)：グリシジル基を含まないその他の共重合可能
な重合性単量体97.85〜25重量％ を反応させることを特徴とするグラフト共重合
体樹脂の製造方法。 ２ セルロースアセテートブチレートがアセチル
基1.8〜15重量％、ブチリル基36〜58重量％、お
よびヒドロキシル基５重量％以下を含むものであ
る特許請求の範囲第１項記載のグラフト共重合体
樹脂の製造方法。 ３ ヒドロキシル基含有重合性単量体が２−ヒド
ロキシエチルアクリレート、２−ヒドロキシエチ
ルメタクリレート、２−ヒドロキシプロピルアク
リレート、および２−ヒドロキシプロピルメタク
リレートから選ばれる１種以上のものである特許
請求の範囲第１項または第２項記載のグラフト共
重合体樹脂の製造方法。[Claims] 1 (A): Cellulose acetate butyrate 2-60
Weight%, (B): 0.05 to 15% by weight of one or more acid anhydrides containing no polymerizable unsaturated bonds selected from succinic anhydride, phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride (C): Hydroxyl A graft copolymer characterized by reacting 0.1 to 70% by weight of a group-containing polymerizable monomer and (D): 97.85 to 25% by weight of another copolymerizable monomer that does not contain a glycidyl group. Method for producing combined resin. 2. The method for producing a graft copolymer resin according to claim 1, wherein the cellulose acetate butyrate contains 1.8 to 15% by weight of acetyl groups, 36 to 58% by weight of butyryl groups, and 5% by weight or less of hydroxyl groups. 3. Claim 1, wherein the hydroxyl group-containing polymerizable monomer is one or more selected from 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. A method for producing a graft copolymer resin according to item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21116387A JPS6454014A (en) | 1987-08-25 | 1987-08-25 | Production of graft copolymer resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21116387A JPS6454014A (en) | 1987-08-25 | 1987-08-25 | Production of graft copolymer resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6454014A JPS6454014A (en) | 1989-03-01 |
| JPH058922B2 true JPH058922B2 (en) | 1993-02-03 |
Family
ID=16601442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21116387A Granted JPS6454014A (en) | 1987-08-25 | 1987-08-25 | Production of graft copolymer resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6454014A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004058883A1 (en) * | 2002-12-26 | 2004-07-15 | Mitsubishi Rayon Co., Ltd. | Polymer composition, composite fiber, processes for producing these, and woven fabric |
| CN102432777B (en) * | 2011-08-29 | 2013-04-10 | 华南理工大学 | Method for modifying cellulose acetate butyrate (CAB) for electro-silvered simulating coating |
| JP5560317B2 (en) * | 2012-12-04 | 2014-07-23 | 大日本塗料株式会社 | Painted body |
| JP5564592B1 (en) * | 2013-03-19 | 2014-07-30 | 大日本塗料株式会社 | Resin composition and coated body using the same |
| WO2014087698A1 (en) * | 2012-12-04 | 2014-06-12 | 大日本塗料株式会社 | Coated article and resin composition used in same |
| CN104877082A (en) * | 2015-06-02 | 2015-09-02 | 清远雅克化工有限公司 | Preparation method of CAB (cellulose acetate butyrate) graft modified hydroxy acrylic resin for electrosilvering paint |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5048031A (en) * | 1973-08-31 | 1975-04-28 |
-
1987
- 1987-08-25 JP JP21116387A patent/JPS6454014A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5048031A (en) * | 1973-08-31 | 1975-04-28 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6454014A (en) | 1989-03-01 |
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