JPH04351615A - Graft copolymer and preparation thereof - Google Patents
Graft copolymer and preparation thereofInfo
- Publication number
- JPH04351615A JPH04351615A JP12437391A JP12437391A JPH04351615A JP H04351615 A JPH04351615 A JP H04351615A JP 12437391 A JP12437391 A JP 12437391A JP 12437391 A JP12437391 A JP 12437391A JP H04351615 A JPH04351615 A JP H04351615A
- Authority
- JP
- Japan
- Prior art keywords
- meth
- polymerization
- polymer
- graft copolymer
- acrylamide
- 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.)
- Pending
Links
- 229920000578 graft copolymer Polymers 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 3
- 239000000178 monomer Substances 0.000 claims abstract description 46
- 150000002978 peroxides Chemical class 0.000 claims abstract description 23
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 23
- 239000008199 coating composition Substances 0.000 claims description 27
- 239000000049 pigment Substances 0.000 claims description 24
- 239000003505 polymerization initiator Substances 0.000 claims description 24
- 150000003926 acrylamides Chemical class 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- 229920005989 resin Polymers 0.000 abstract description 23
- 239000011347 resin Substances 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 20
- 239000011248 coating agent Substances 0.000 abstract description 17
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 abstract description 11
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 239000003999 initiator Substances 0.000 abstract 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 35
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- 238000007334 copolymerization reaction Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- -1 N-isopropylmethacrylamide Amide Chemical class 0.000 description 11
- 239000004342 Benzoyl peroxide Substances 0.000 description 10
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 10
- 235000019400 benzoyl peroxide Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- WLPAQAXAZQUXBG-UHFFFAOYSA-N 1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCC1 WLPAQAXAZQUXBG-UHFFFAOYSA-N 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 238000010559 graft polymerization reaction Methods 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- RESPXSHDJQUNTN-UHFFFAOYSA-N 1-piperidin-1-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCCCC1 RESPXSHDJQUNTN-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 229920000180 alkyd Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- OVHHHVAVHBHXAK-UHFFFAOYSA-N n,n-diethylprop-2-enamide Chemical compound CCN(CC)C(=O)C=C OVHHHVAVHBHXAK-UHFFFAOYSA-N 0.000 description 4
- ZIWDVJPPVMGJGR-UHFFFAOYSA-N n-ethyl-2-methylprop-2-enamide Chemical compound CCNC(=O)C(C)=C ZIWDVJPPVMGJGR-UHFFFAOYSA-N 0.000 description 4
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 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
- 238000010526 radical polymerization reaction 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- SWPMNMYLORDLJE-UHFFFAOYSA-N n-ethylprop-2-enamide Chemical compound CCNC(=O)C=C SWPMNMYLORDLJE-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 2
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- RASDUGQQSMMINZ-UHFFFAOYSA-N 2-methyl-1-piperidin-1-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCCCC1 RASDUGQQSMMINZ-UHFFFAOYSA-N 0.000 description 2
- LVCMKNCJDCTPIB-UHFFFAOYSA-N 2-methyl-1-pyrrolidin-1-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCCC1 LVCMKNCJDCTPIB-UHFFFAOYSA-N 0.000 description 2
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- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-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
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000000429 sodium aluminium silicate Substances 0.000 description 1
- 235000012217 sodium aluminium silicate Nutrition 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- QXKXDIKCIPXUPL-UHFFFAOYSA-N sulfanylidenemercury Chemical compound [Hg]=S QXKXDIKCIPXUPL-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はグラフト共重合体及びそ
の製造方法に関する。更に詳しくは、特定のＮ−置換（
メタ）アクリルアミド系重合体のグラフト共重合体、過
酸化物系重合開始剤により重合するグラフト共重合体の
製造方法及び塗料用組成物並びに顔料含有塗料用組成物
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a graft copolymer and a method for producing the same. More specifically, certain N-substitutions (
The present invention relates to a graft copolymer of a meth)acrylamide polymer, a method for producing the graft copolymer polymerized using a peroxide polymerization initiator, a coating composition, and a pigment-containing coating composition.
【０００２】0002
【従来の技術】本発明において、基本的な基材として使
用する特定のＮ−置換（メタ）アクリルアミド系重合体
は、水溶液中において温度によりそれ自身の性質が親水
性から疎水性に変化する。より具体的には低温ほど親水
的であり、加温により疎水的となり場合によっては不溶
化して水溶液が白濁し、曇点現象を呈する。そのような
性質を利用することにより水の分離による濃縮、脱水、
温度による溶質の透過制御、吸着分離、水蒸気の吸収・
放出、防曇等各種用途への応用が検討されている。BACKGROUND OF THE INVENTION In the present invention, the specific N-substituted (meth)acrylamide polymer used as a basic base material changes its properties from hydrophilic to hydrophobic depending on the temperature in an aqueous solution. More specifically, the lower the temperature, the more hydrophilic it is, and upon heating, it becomes hydrophobic and, in some cases, becomes insolubilized, making the aqueous solution cloudy and exhibiting a cloud point phenomenon. By utilizing such properties, it is possible to concentrate, dehydrate, and
Temperature-based solute permeation control, adsorption separation, water vapor absorption and
Applications are being considered for various purposes such as release and anti-fogging.
【０００３】0003
【発明が解決しようとする課題】それらいづれの用途に
おいても、使用に当たっては水不溶化処理することが必
要であるが、従来の架橋剤との共重合、水不溶性単量体
との共重合等の方法では肝心のＮ−置換（メタ）アクリ
ルアミド系重合体自体の性質が変化してしまい十分な機
能を発揮するに至っていない。[Problem to be solved by the invention] In any of these applications, water insolubilization treatment is required before use, but copolymerization with conventional crosslinking agents, copolymerization with water-insoluble monomers, etc. In this method, the essential properties of the N-substituted (meth)acrylamide polymer itself change, and it is not able to exhibit sufficient functionality.
【０００４】0004
【課題を解決するための手段】本発明者らは上記した点
に鑑み鋭意検討した結果、Ｎ−置換（メタ）アクリルア
ミド系重合体の共存下に、過酸化物系重合開始剤により
ラジカル重合可能な単量体を重合し、これをＮ−置換（
メタ）アクリルアミド系重合体にグラフト共重合せしめ
ることにより、優れた特性を有するグラフト共重合体を
製造することができ、かつ前記した用途以外にも塗料用
組成物、顔料含有塗料用組成物として有用であることを
見い出し、本発明に到達した。即ち、本発明は[Means for Solving the Problem] As a result of intensive studies in view of the above points, the present inventors have found that radical polymerization is possible with a peroxide polymerization initiator in the coexistence of an N-substituted (meth)acrylamide polymer. The monomer is polymerized, and this is N-substituted (
By graft copolymerizing a meth)acrylamide-based polymer, a graft copolymer with excellent properties can be produced, and in addition to the above-mentioned uses, it is useful as a coating composition and a pigment-containing coating composition. We have discovered that this is the case, and have arrived at the present invention. That is, the present invention
【０００
５】一般式（Ｉ）または一般式（ＩＩ）で表される000
5] Represented by general formula (I) or general formula (II)
【化３】[C3]
【化４】
Ｎ−置換（メタ）アクリルアミド誘導体を重合してなる
Ｎ−置換（メタ）アクリルアミド系重合体に、ラジカル
重合可能な単量体をグラフト共重合せしめてなるグラフ
ト共重合体であり、過酸化物系重合開始剤存在下、この
Ｎ−置換（メタ）アクリルアミド系重合体にラジカル重
合可能な単量体をグラフト共重合せしめるグラフト共重
合体の製造方法、であり、該グラフト共重合体を含有し
てなる塗料用組成物、並びに、該塗料用組成物に、顔料
を分散せしめてなる顔料含有塗料用組成物、をを要旨と
するものである。[Chemical formula 4] A graft copolymer obtained by graft copolymerizing a radically polymerizable monomer to an N-substituted (meth)acrylamide polymer obtained by polymerizing an N-substituted (meth)acrylamide derivative, A method for producing a graft copolymer, which comprises graft copolymerizing a radically polymerizable monomer to the N-substituted (meth)acrylamide polymer in the presence of a peroxide polymerization initiator. The gist of the present invention is to provide a coating composition containing the following: and a pigment-containing coating composition obtained by dispersing a pigment in the coating composition.
【０００６】本発明で使用される特定のＮ−置換（メタ
）アクリルアミド誘導体とは、上記のごとき一般式（Ｉ
）または一般式（ＩＩ）で表されるＮ−アルキルまたは
Ｎ−アルキレン置換（メタ）アクリルアミドであって、
具体的には、例えばＮ−エチルアクリルアミド、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、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ−エチ
ルメタクリルアミド、Ｎ−メチル−Ｎ−エチルアクリル
アミド、Ｎ−イソプロピルアクリルアミド、Ｎ−ｎ−プ
ロピルアクリルアミド、Ｎ−イソプロピルメタクリルア
ミド、Ｎ−ｎ−プロピルメタクリルアミド、Ｎ−アクリ
ロイルピロリジン、Ｎ−メタクリロイルピロリジン、Ｎ
−アクリロイルピペリジン、Ｎ−メタクリロイルピペリ
ジン、Ｎ−アクリロイルヘキサヒドロアゼピン、Ｎ−ア
クリロイルモルホリン等をあげることができる。The specific N-substituted (meth)acrylamide derivative used in the present invention has the general formula (I
) or an N-alkyl or N-alkylene substituted (meth)acrylamide represented by general formula (II),
Specifically, for example, N-ethylacrylamide, N,N
-dimethylacrylamide, N,N-dimethylmethacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide, N-isopropylacrylamide, N-n-propylacrylamide, N-isopropylmethacrylamide Amide, N-n-propylmethacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N
-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, and the like.
【０００７】そして、上記した単量体の中で、特に単量
体の重合体が水溶液中で感温性を示すもの−即ち低温に
おいては親水性であり加温してゆくと疎水性に変化する
もの−で、かつ液体状のモノマーが好ましい。具体的に
は、例えばＮ−エチルアクリルアミド、Ｎ−メチル−Ｎ
−エチルアクリルアミド、Ｎ，Ｎ−ジエチルアクリアミ
ド、Ｎ−エチルメタクリルアミド、Ｎ−メチル−Ｎ−エ
チルメタクリルアミド、Ｎ−ｎ−プロピルアクリルアミ
ド、Ｎ−ｎ−プロピルメタクリルアミド、Ｎ−イソプロ
ピルアクリルアミド、Ｎ−イソプロピルメタクリルアミ
ド、Ｎ−アクリロイルピロリジン、Ｎ−メタクリロイル
ピロリジン、Ｎ−アクリロイルピペリジン、Ｎ−メタク
リロイルピペリジン等を特に好ましいものとしてあげる
ことができる。なお、更に該単量体の重合体が水溶液中
で曇点を有するものとして、例えばＮ，Ｎ−ジエチルア
クリルアミド、Ｎ−エチルメタクリルアミド、Ｎ−イソ
プロピルアクリルアミド、Ｎ−ｎ−プロピルアクリルア
ミド、Ｎ−アクリロイルピロリジン、Ｎ−アクリロイル
ピペリジン等をあげることができる。本発明におけるＮ
−置換（メタ）アクリルアミド系重合体とは、上記のＮ
−置換（メタ）アクリルアミドの１種または２種以上の
重合体であり、更には共重合可能な単量体を共重合した
ものでもよい。重合する方法としては通常のラジカル重
合により行えばよい。[0007] Among the above-mentioned monomers, polymers of monomers in particular exhibit temperature sensitivity in aqueous solutions - that is, they are hydrophilic at low temperatures and change to hydrophobic when heated. A liquid monomer is preferred. Specifically, for example, N-ethylacrylamide, N-methyl-N
-Ethylacrylamide, N,N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylmethacrylamide, N-n-propylacrylamide, N-n-propylmethacrylamide, N-isopropylacrylamide, N- Isopropylmethacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine and the like are particularly preferred. In addition, examples of polymers of the monomer having a clouding point in an aqueous solution include, for example, N,N-diethylacrylamide, N-ethylmethacrylamide, N-isopropylacrylamide, N-n-propylacrylamide, and N-acryloyl. Examples include pyrrolidine and N-acryloylpiperidine. N in the present invention
-Substituted (meth)acrylamide polymer refers to the above N
- It is a polymer of one type or two or more types of substituted (meth)acrylamides, and may also be a copolymer of copolymerizable monomers. The polymerization may be carried out by ordinary radical polymerization.
【０００８】例えば、該Ｎ−置換（メタ）アクリルアミ
ドの１種または２種以上をそのまま、または、適当な溶
媒で所望の濃度に希釈して、例えば水溶媒の場合は、５
〜８０％程度の水溶液としたものを窒素等の不活性ガス
で充分置換した後、過硫酸アンモニウム単独またはこれ
と亜硫酸水素ナトリウムを併用したものをそれぞれ ０
．１〜５％、０．１ 〜５％程度存在させ、２０〜８０
℃で３０ｍｉｎ 〜１００ ｈｒ程度重合させることに
より、Ｎ−置換（メタ）アクリルアミドの重合体の対応
する濃度の水溶液が容易に得られるのである。For example, one or more of the N-substituted (meth)acrylamides may be used as is or diluted to a desired concentration with an appropriate solvent, for example, in the case of an aqueous solvent, 5
After sufficiently replacing the aqueous solution with a concentration of ~80% with an inert gas such as nitrogen, ammonium persulfate alone or a combination of ammonium persulfate and sodium hydrogen sulfite was added to each solution.
．． 1 to 5%, 0.1 to 5%, 20 to 80%
By polymerizing at a temperature of 30 min to 100 hr, an aqueous solution of the N-substituted (meth)acrylamide polymer at a corresponding concentration can be easily obtained.
【０００９】本発明は、過酸化物系重合開始剤存在下、
斯かるＮ−置換（メタ）アクリルアミド系重合体に、ラ
ジカル重合可能な単量体をグラフト共重合せしめるもの
であるが、本発明で使用される過酸化物系重合開始剤は
、有機系及び無機系のどちらの過酸化物系重合開始剤で
もよく、これらの過酸化物系重合開始剤と還元剤との組
合せによるレドックス系重合開始剤を使用してもよい。
具体的には、例えば有機過酸化物系重合開始剤としては
、メチルエチルケトンパーオキサイド、シクロヘキサノ
ンパーオキサイド等のケトンパーオキサイド類；アセチ
ルパーオキサイド、オクタノイルパーオキサイド、イソ
ノナノイルパーオキサイド、ベンゾイルパーオキサイド
、アセチルシクロヘキサンスルホニルパーオキサイド等
のジアシルパーオキサイド類；ｔ−ブチルヒドロパーオ
キサイド、ジ−イソプロピルベンゼンヒドロパーオキサ
イト、ｐ−メンタンヒドロパーオキサイド等のヒドロパ
ーオキサイド類；ジ−ｔ−ブチルパーオキサイド、ｔ−
ブチル−α−クミルパーオキサイド、ジクミルパーオキ
サイド等のジアルキルパーオキサイド類；１，１−ビス
−ｔ−ブチルパーオキシ−３，３，５−トリメチルシク
ロヘキサン、２，２−ビス（ｔ−ブチルパーオキシ）ブ
タン等のパーオキシケタール類；ｔ−ブチルパーオキシ
アセテート、ｔ−ブチルパーオキシベンゾエート、ジ−
ｔ−ブチルパーオキシフタレート等のアルキルパーエス
テル類；ジ−２−エチルヘキシルパーオキシジカーボネ
ート、ジ−イソプロピルパーオキシジカーボネート、ジ
−３−メトキシブチルパーオキシジカーボネート等のパ
ーオキシカーボネート類及びコハク酸パーオキサイド等
の水溶性パーオキサイド等があげられる。[0009] In the present invention, in the presence of a peroxide polymerization initiator,
The N-substituted (meth)acrylamide-based polymer is graft-copolymerized with a radically polymerizable monomer, and the peroxide-based polymerization initiator used in the present invention can be organic or inorganic. Any peroxide-based polymerization initiator may be used, and a redox-based polymerization initiator formed by a combination of these peroxide-based polymerization initiators and a reducing agent may be used. Specifically, for example, organic peroxide polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; acetyl peroxide, octanoyl peroxide, isononanoyl peroxide, benzoyl peroxide, Diacyl peroxides such as acetylcyclohexane sulfonyl peroxide; hydroperoxides such as t-butyl hydroperoxide, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide; di-t-butyl peroxide, t −
Dialkyl peroxides such as butyl-α-cumyl peroxide and dicumyl peroxide; 1,1-bis-t-butylperoxy-3,3,5-trimethylcyclohexane, 2,2-bis(t-butylperoxide) Peroxyketals such as oxy)butane; t-butyl peroxyacetate, t-butyl peroxybenzoate, di-
Alkyl peresters such as t-butyl peroxyphthalate; peroxycarbonates such as di-2-ethylhexyl peroxydicarbonate, di-isopropyl peroxydicarbonate, di-3-methoxybutyl peroxydicarbonate, and succinic acid. Examples include water-soluble peroxides such as peroxide.
【００１０】一方、無機過酸化物系重合開始剤としては
、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリ
ウム等の過硫酸塩類、過酸化水素及び過酸化ニッケル等
の金属過酸化物類等があげられる。さらに、上記過酸化
物系重合開始剤と組み合わせるレドックス系重合開始剤
の還元剤としては、具体的には例えば亜硫酸塩、亜硫酸
水素塩、鉄、銅、コバルト、等の低イオン化塩；トリエ
チルホウ素、ジエチル亜鉛等の有機金属化合物；トリエ
チルアミン、ジメチルアニリン等のアミン誘導体、アル
ドース、ケトース等の還元糖等があげられる。また、上
記した過酸化物系重合開始剤並びに過酸化物系重合開始
剤を用いたレドックス系重合開始剤は２種以上併用して
使用してもよい。本発明でＮ−置換（メタ）アクリルア
ミド系重合体にグラフトさせるラジカル重合可能な単量
体としては、前記した単量体、下記の親水性単量体、イ
オン性単量体、親油性単量体の中から選ばれた１種以上
の単量体をあげることができる。On the other hand, examples of inorganic peroxide polymerization initiators include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate, and metal peroxides such as hydrogen peroxide and nickel peroxide. . Furthermore, the reducing agent for the redox polymerization initiator combined with the above peroxide polymerization initiator includes, for example, low ionized salts such as sulfite, hydrogen sulfite, iron, copper, and cobalt; triethyl boron, Examples include organometallic compounds such as diethylzinc; amine derivatives such as triethylamine and dimethylaniline; and reducing sugars such as aldose and ketose. Furthermore, two or more of the above-described peroxide-based polymerization initiators and redox-based polymerization initiators using peroxide-based polymerization initiators may be used in combination. In the present invention, the radically polymerizable monomers to be grafted onto the N-substituted (meth)acrylamide-based polymer include the above-mentioned monomers, the following hydrophilic monomers, ionic monomers, and lipophilic monomers. One or more monomers selected from the body can be mentioned.
【００１１】具体的にはラジカル重合可能な親水性単量
体として、例えばジアセトンアクリルアミド、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、Ｎ−エチルメタクリルアミド、Ｎ−エチルアク
リルアミド、Ｎ，Ｎ−ジエチルアクリルアミド、Ｎ−プ
ロピルアクリルアミド、Ｎ−アクリロイルピロリジン、
Ｎ−アクリロイルピペリジン、Ｎ−アクリロイルモルホ
リン、ヒドロキシエチルメタクリレート、ヒドロキシエ
チルアクリレート、ヒドロキシプロピルメタクリレート
、ヒドロキシプロピルアクリレート、各種のメトキシポ
リエチレングリコール（メタ）アクリレート、Ｎ−ビニ
ル−２−ピロリドン等をあげることができる。Specifically, examples of radically polymerizable hydrophilic monomers include diacetone acrylamide, N,N-
Dimethylacrylamide, N,N-dimethylmethacrylamide, N-ethylmethacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-propylacrylamide, N-acryloylpyrrolidine,
Examples include N-acryloylpiperidine, N-acryloylmorpholine, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxypolyethylene glycol (meth)acrylates, and N-vinyl-2-pyrrolidone.
【００１２】ラジカル重合可能なイオン性単量体として
は、例えばアクリル酸、メタクリル酸、ビニルスルホン
酸、アリルスルホン酸、メタクリルスルホン酸、スチレ
ンスルホン酸、２−アクリルアミド−２−フェニルプロ
パンスルホン酸、２−アクリルアミド−２−メチルプロ
パンスルホン酸等の酸及びそれらの塩、Ｎ，Ｎ−ジメチ
ルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアミ
ノエチルメタクリレート、Ｎ，Ｎ−ジメチルアハノエチ
ルアクリレート、Ｎ，Ｎ−ジメチルアミノプロピルメタ
クリルアミド、Ｎ，Ｎ−ジメチルアミノプロピルアクリ
ルアミド等のアミン及びそれらの塩等をあげることがで
きる。Examples of radically polymerizable ionic monomers include acrylic acid, methacrylic acid, vinylsulfonic acid, allylsulfonic acid, methacrylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, -Acids such as acrylamide-2-methylpropanesulfonic acid and their salts, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylahanoethyl acrylate, N,N-dimethylamino Examples include amines such as propylmethacrylamide and N,N-dimethylaminopropylacrylamide, and salts thereof.
【００１３】ラジカル重合可能な親油性単量体としては
、例えばＮ，Ｎ−ジ−ｎ−プロピルアクリルアミド、Ｎ
−ｎ−ブチルアクリルアミド、Ｎ−ｎ−ヘキシルアクリ
ルアミド、Ｎ−ｎ−ヘキシルメタクリルアミド、Ｎ−ｎ
−オクチルアクリルアミド、Ｎ−ｎ−オクチルメタクリ
ルアミド、Ｎ−ｔｅｒｔ−オクチルアクリルアミド、Ｎ
−ドデシルアクリルアミド、Ｎ−ｎ−ドデシルメタクリ
ルアミド等のＮ−アルキル（メタ）アクリルアミド誘導
体、Ｎ，Ｎ−ジグリシジルアクリルアミド、Ｎ，Ｎ−ジ
グリシジルメタクリルアミド、Ｎ−（４−グリシドキシ
ブチル）アクリルアミド、Ｎ−（４−グリシドキシブチ
ル）メタクリルアミド、Ｎ−（５−グリシドキシペンチ
ル）アクリルアミド、Ｎ−（６−グリシドキシヘキシル
）アクリルアミド等のＮ−（ω−グリシドキシアルキル
）（メタ）アクリルアミド誘導体、メチル（メタ）アク
リレート、エチル（メタ）アクリレート、ブチル（メタ
）アクリレート、ラウリル（メタ）アクリレート，２−
エチルヘキシル（メタ）アクリレート、グリシジル（メ
タ）アクリレート等の（メタ）アクリレート誘導体、ア
クリロニトリル、メタクリロニトリル、酢酸ビニル、塩
化ビニル、塩化ビニリデン、エチレン、プロピレン、ブ
テン等のオレフィン類、スチレン、ジビニルベンゼン、
α−メチルスチレン、ブタジエン、イソプレン等をあげ
ることができる。のである。Examples of radically polymerizable lipophilic monomers include N,N-di-n-propylacrylamide and N,N-di-n-propylacrylamide.
-n-butylacrylamide, N-n-hexyl acrylamide, N-n-hexylmethacrylamide, N-n
-octylacrylamide, N-n-octylmethacrylamide, N-tert-octylacrylamide, N
-Dodecyl acrylamide, N-alkyl (meth)acrylamide derivatives such as N-n-dodecylmethacrylamide, N,N-diglycidyl acrylamide, N,N-diglycidyl methacrylamide, N-(4-glycidoxybutyl)acrylamide , N-(ω-glycidoxyalkyl)( meth)acrylamide derivatives, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, 2-
(meth)acrylate derivatives such as ethylhexyl (meth)acrylate and glycidyl (meth)acrylate, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, olefins such as ethylene, propylene, and butene, styrene, divinylbenzene,
Examples include α-methylstyrene, butadiene, and isoprene. It is.
【００１４】本発明のグラフト共重合体を構成する上記
した成分の構成比は、使用する成分の性質により変化し
、一概には規定できないが、概ね前記一般式（Ｉ）及び
（ＩＩ）で表せる特定のＮ−置換（メタ）アクリルアミ
ド誘導体を重合してなるＮ−置換（メタ）アクリルアミ
ド系重合体０．１〜９９．９重量％、ラジカル重合可能
な単量体９９．９〜０．１重量％、及び過酸化物系重合
開始剤がグラフトする単量体に対して０．０１〜２０重
量％であり、さらに好ましくは、Ｎ−置換（メタ）アク
リルアミド系重合体１〜９５重量％、ラジカル重合可能
な単量体９５〜１重量％、及び過酸化物系重合開始剤が
グラフトする単量体に対して０．０３〜１０重量％の構
成比である。なお、上記した成分の構成比でグラフト共
重合体を合成する際にグラフト効率を向上するために下
記する溶媒により適宜希釈して使用してもよい。即ち、
重合溶液を希釈することによりラジカル重合可能な単量
体同志の重合率を低下させることとなりＮ−置換（メタ
）アクリルアミド系重合体へのグラフト効率を向上させ
ることが可能となるのである。[0014] The composition ratio of the above-mentioned components constituting the graft copolymer of the present invention varies depending on the properties of the components used and cannot be unconditionally defined, but can generally be represented by the above general formulas (I) and (II). 0.1 to 99.9% by weight of an N-substituted (meth)acrylamide polymer obtained by polymerizing a specific N-substituted (meth)acrylamide derivative, and 99.9 to 0.1% by weight of a radically polymerizable monomer. %, and the peroxide polymerization initiator is 0.01 to 20% by weight based on the monomer to be grafted, more preferably 1 to 95% by weight of the N-substituted (meth)acrylamide polymer, and the radical The composition ratio is 95 to 1% by weight of the polymerizable monomer and 0.03 to 10% by weight based on the monomer to be grafted with the peroxide polymerization initiator. In addition, in order to improve the grafting efficiency when synthesizing a graft copolymer with the composition ratio of the above-mentioned components, it may be used after being diluted appropriately with the following solvent. That is,
By diluting the polymerization solution, the polymerization rate of radically polymerizable monomers can be reduced, making it possible to improve the efficiency of grafting onto the N-substituted (meth)acrylamide polymer.
【００１５】グラフト重合する際使用されるかかる溶媒
としては、具体的には水、メタノール、エタノール、プ
ロパノール、ブタノール等のアルコール類；アセトン、
メチルエチルケトン、シクロヘキサノン等のケトン類；
クロロホルム、メチレンジクロライド等のハロゲン化炭
化水素類；ベンゼン、トルエン等の芳香族炭化水素類；
エチレングリコールメチルエーテル、エチルエーテル、
ブチルエーテル等の各種セルソルブ類；酢酸エチル、ク
ロロ酢酸エチル等の各種エステル類；Ｎ，Ｎ−ジメチル
ホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド等のアミ
ド類；１，４−ジオキサン、テトラヒドロフラン等の環
状エーテル類；ジメチルスルホキシド、Ｎ−メチルピロ
リドン、ジグライム等の鎖状グリコール類等及びピリジ
ン等の塩基性溶媒があげられる。上記重合溶媒は単独で
もまたは相溶性があれば２種以上混合して使用してもよ
い。その時のグラフト共重合組成物濃度は１重量％以上
である。また、重合の際、上記溶媒はそのまま使用して
もよいし、溶存酸素濃度を少なくした状態、具体的には
窒素ガスのような不活性ガスで置換して使用してもよい
。しかし、重合を速やかに行わせ、グラフト率を向上さ
せるには窒素等による不活性ガス置換を行い溶存酸素濃
度を低下させる方が好ましい。次に上記したＮ−置換（
メタ）アクリルアミド系重合体（ の共存下 ）に過酸
化物系重合開始剤によりラジカル重合可能な単量体をグ
ラフト重合を行いグラフト共重合体を製造する方法につ
いて述べる。[0015] Specific examples of such solvents used in graft polymerization include water, alcohols such as methanol, ethanol, propanol, and butanol; acetone;
Ketones such as methyl ethyl ketone and cyclohexanone;
Halogenated hydrocarbons such as chloroform and methylene dichloride; Aromatic hydrocarbons such as benzene and toluene;
ethylene glycol methyl ether, ethyl ether,
Various cellosolves such as butyl ether; various esters such as ethyl acetate and ethyl chloroacetate; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; cyclic ethers such as 1,4-dioxane and tetrahydrofuran; Examples include chain glycols such as dimethyl sulfoxide, N-methylpyrrolidone and diglyme, and basic solvents such as pyridine. The above polymerization solvents may be used alone or in combination of two or more if they are compatible. The concentration of the graft copolymer composition at that time is 1% by weight or more. Further, during polymerization, the above-mentioned solvent may be used as it is, or may be used in a state where the dissolved oxygen concentration is reduced, specifically, after being replaced with an inert gas such as nitrogen gas. However, in order to speed up the polymerization and improve the grafting rate, it is preferable to perform inert gas substitution with nitrogen or the like to lower the dissolved oxygen concentration. Next, the above N-substitution (
A method for producing a graft copolymer by graft polymerizing a radically polymerizable monomer onto a meth)acrylamide polymer (in the presence of ) using a peroxide polymerization initiator will be described.
【００１６】グラフト重合温度は任意に設定してもよい
し、重合途中で重合温度を変化させても差し支えない。
重合温度は一概には決められないが単一過酸化物系重合
開始剤の場合には、概ね２０〜９０℃の範囲であり、レ
ドックス系重合開始剤の場合にはより低く概ね−１０〜
５０℃の範囲である。重合は、重合溶媒の沸点より低い
温度で行うことが好ましい。重合時間は特に限定はない
が、概ね１〜４８時間である。重合の際は静置状態、振
とうさせながらあるいは重合溶液を撹拌しながら行って
よく特に制約はない。より実際的は、Ｎ−置換（メタ）
アクリルアミド系重合体を製造した後、引き続いてこの
グラフト重合を行うことが好ましい。なお、Ｎ−置換（
メタ）アクリルアミド系重合体の製造はＮ−置換（メタ
）アクリルアミド誘導体を、すでに述べたとおりの通常
の方法により重合して行えばよい。なお、重合方法とし
てはラジカル重合及びイオン重合のいづれも採用が可能
であるが、装置上簡便に行えるラジカル重合が好ましい
。重合様式としては溶液重合、懸濁重合、乳化重合、析
出重合等いづれの方法も採用できる。そのようにして製
造したＮ−置換（メタ）アクリルアミド系重合体は溶媒
を留去した固体状のものでも、また溶媒に溶解している
溶液状のものでもいづれも使用できる。The graft polymerization temperature may be set arbitrarily, and the polymerization temperature may be changed during the polymerization. The polymerization temperature cannot be determined unconditionally, but in the case of a single peroxide polymerization initiator, it is generally in the range of 20 to 90°C, and in the case of a redox polymerization initiator, it is lower, generally in the range of -10 to 90°C.
The temperature range is 50°C. The polymerization is preferably carried out at a temperature lower than the boiling point of the polymerization solvent. The polymerization time is not particularly limited, but is approximately 1 to 48 hours. The polymerization may be carried out in a stationary state, while being shaken, or while stirring the polymerization solution, and there are no particular restrictions. More practically, N-substitution (meta)
After producing the acrylamide polymer, it is preferable to carry out this graft polymerization subsequently. Note that N-substitution (
The meth)acrylamide-based polymer may be produced by polymerizing an N-substituted (meth)acrylamide derivative by the usual method as described above. Incidentally, as the polymerization method, both radical polymerization and ionic polymerization can be employed, but radical polymerization is preferred because it can be easily carried out using an apparatus. As the polymerization mode, any method such as solution polymerization, suspension polymerization, emulsion polymerization, precipitation polymerization, etc. can be adopted. The N-substituted (meth)acrylamide polymer thus produced can be used either in the form of a solid obtained by distilling off the solvent, or in the form of a solution dissolved in a solvent.
【００１７】ここで、前記したとおり、Ｎ−置換（メタ
）アクリルアミド系重合体を製造後、直ちにグラフト共
重合を行う場合には、溶液重合にてＮ−置換（メタ）ア
クリルアミド系重合体を製造後、グラフト共重合すべき
単量体を添加し引き続きグラフト共重合体の製造を行え
ばよい。グラフト共重合体を効率よく行わせる好ましい
態様は、Ｎ−置換（メタ）アクリルアミド系重合体の水
溶液中で該重合体が水不溶性となる単量体を無機過酸化
物を用いて重合することである。かくすることにより、
高い効率でグラフト重合でき、得られるグラフト共重合
体は水不溶の析出重合体となり、安定なエマルションを
形成することができるからである。一方、溶媒に溶解し
た状態でグラフト共重合体を製造することもできる。こ
の場合は、グラフト共重合すべき単量体の重合体を溶解
する溶剤を使用して、Ｎ−置換（メタ）アクリルアミド
系重合体の製造及びそれに引き続くグラフト共重合を行
えばよい。As mentioned above, when graft copolymerization is carried out immediately after producing the N-substituted (meth)acrylamide-based polymer, the N-substituted (meth)acrylamide-based polymer is produced by solution polymerization. Thereafter, monomers to be graft copolymerized may be added to continue producing the graft copolymer. A preferred embodiment for efficient graft copolymerization is to polymerize a monomer that makes the polymer water-insoluble in an aqueous solution of an N-substituted (meth)acrylamide polymer using an inorganic peroxide. be. By doing so,
This is because graft polymerization can be carried out with high efficiency, and the resulting graft copolymer becomes a water-insoluble precipitated polymer and can form a stable emulsion. On the other hand, the graft copolymer can also be produced in a state dissolved in a solvent. In this case, the N-substituted (meth)acrylamide polymer may be produced and the subsequent graft copolymerization may be carried out using a solvent that dissolves the monomer polymer to be graft copolymerized.
【００１８】なお、上記した方法で製造されたグラフト
共重合体は、Ｎ−置換（メタ）アクリルアミド系重合体
やラジカル重合可能な単量体の重合体からなる、グラフ
トしていない単独重合体との混合物になっているが、通
常は単独重合体を分離せずにそのまま使用してよい。も
ちろん、目的によっては、分離することもできるが、グ
ラフト共重合体を分離する場合には、下記する再沈法に
よって行えばよい。即ち、有機溶媒中でグラフト重合し
た場合は重合溶液をそのままエーテル等のグラフト共重
合体の沈澱溶媒中に落し、目的のグラフト共重合体を沈
澱させ、濾過した後、濾過された重合物をＮ−置換（メ
タ）アクリルアミド系重合体及びラジカル重合可能な単
量体の重合体を溶解するような有機溶媒で洗浄を行いグ
ラフト共重合体を分離すればよい。また、水中でグラフ
ト重合した場合は重合溶液を凍結乾燥させた後、ベンゼ
ン等の有機溶媒に溶解させて有機溶媒中でグラフト重合
した時のようにエーテル等のグラフト共重合体の沈澱溶
媒中に落しグラフト共重合体を沈澱させ、濾過した後、
濾過された重合物をＮ−置換（メタ）アクリルアミド系
重合体及びラジカル重合可能な単量体の重合体を溶解す
るような有機溶媒で洗浄を行いグラフト共重合体を分離
すればよい。The graft copolymer produced by the above method is a non-grafted homopolymer consisting of an N-substituted (meth)acrylamide polymer or a polymer of radically polymerizable monomers. However, the homopolymer can usually be used as it is without separating it. Of course, separation can be performed depending on the purpose, but when separating the graft copolymer, it may be carried out by the reprecipitation method described below. That is, when graft polymerization is carried out in an organic solvent, the polymerization solution is directly poured into a graft copolymer precipitation solvent such as ether, the desired graft copolymer is precipitated, and the filtered polymer is filtered with N. - The graft copolymer may be separated by washing with an organic solvent that dissolves the substituted (meth)acrylamide-based polymer and the polymer of radically polymerizable monomers. In addition, when graft polymerization is carried out in water, the polymerization solution is freeze-dried and then dissolved in an organic solvent such as benzene. After precipitating and filtering the drop graft copolymer,
The filtered polymer may be washed with an organic solvent that dissolves the N-substituted (meth)acrylamide polymer and the radically polymerizable monomer to separate the graft copolymer.
【００１９】本発明のグラフト共重合体は、水不溶性の
単量体を選択してグラフト重合し、水不溶化処理されて
いる場合でも、（ 幹ポリマーである ）Ｎ−置換（メ
タ）アクリルアミド系重合体の元来の性質を、そのまま
維持している共重合体であるので、その性質を活かして
、目的に応じて例えば、水不溶化、強靭な膜の形成、微
粒子化等が可能となる。具体的には水の分離、溶質の透
過制御膜、吸着分離樹脂及び膜、水蒸気の吸収・放出膜
、防曇膜等の感温性を利用した用途、更には各種材料と
の相溶性が高いことにより樹脂の相溶化剤、塗料組成物
、顔料分散剤等への応用が出来る。本発明の該グラフト
共重合体を塗料用組成物に応用する場合、単独でも塗料
用樹脂として使用できるが、他の樹脂例えば水性樹脂と
混合して塗料用組成物として使用することもできる。The graft copolymer of the present invention is obtained by graft polymerizing selected water-insoluble monomers, and even when water-insolubilizing treatment is performed, the N-substituted (meth)acrylamide-based polymer (which is the backbone polymer) Since it is a copolymer that maintains the original properties of coalescence, it is possible to take advantage of these properties and make it water insolubilizable, form a tough film, make microparticles, etc., depending on the purpose. Specifically, it is used for water separation, solute permeation control membranes, adsorption separation resins and membranes, water vapor absorption/release membranes, anti-fog membranes, and other applications that utilize temperature sensitivity, and is highly compatible with various materials. As a result, it can be applied to resin compatibilizers, coating compositions, pigment dispersants, etc. When the graft copolymer of the present invention is applied to a coating composition, it can be used alone as a coating resin, but it can also be used as a coating composition by mixing it with another resin, such as an aqueous resin.
【００２０】ここで用いられる水性樹脂とは、水溶性樹
脂あるいは水分散性樹脂であり、アクリル樹脂、ポリエ
ステル樹脂、アルキド樹脂、アクリル変性ポリエステル
樹脂及びアクリル変性アルキド樹脂である。具体的には
例えば、アクリル樹脂としてはアクリル酸、メタクリル
酸、クロトン酸、マレイン酸、フマル酸等のカルボキシ
ル基含有単量体；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、ヒドロキシプロ
ピルアクレート、ヒドロキシプロピルメタクリレート、
ヒドロキシブチルアクリレート、ヒドロキシブチルメタ
クリレート、アリルアルコール等のヒドロキシル基含有
単量体；ジメチルアミノエチルアクリレート、ジメチル
アミノエチルメタクリレート等の含窒素（メタ）アクリ
レート；アクリル酸アミド、メタクリル酸アミド等の（
メタ）アクリル酸アミド；アクリロニトリル、メタクリ
ロニトリル等の（メタ）アクリロニトリル；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
、ｎ−ブチルアクリレート、２−エチルヘキシルアクリ
レート等のアルキル（メタ）アクリレート；スチレン、
α−メチルスチレン、ビニルトルエン等の芳香族系単量
体；エチレン、プロピレン等のα−オレフィン、酢酸ビ
ニル、プロピオン酸ビニル等のビニル化合物及びブタジ
エン、イソプレン等のジエン化合物等の単量体の単独も
しくは任意の組み合わせで重合させて得られるものであ
る。The water-based resin used here is a water-soluble resin or water-dispersible resin, and includes acrylic resin, polyester resin, alkyd resin, acrylic-modified polyester resin, and acrylic-modified alkyd resin. Specifically, for example, acrylic resins include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and fumaric acid; 2-hydroxyethyl acrylate;
2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate,
Hydroxyl group-containing monomers such as hydroxybutyl acrylate, hydroxybutyl methacrylate, and allyl alcohol; Nitrogen-containing (meth)acrylates such as dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate;
Meth)acrylic acid amide; (meth)acrylonitrile such as acrylonitrile and methacrylonitrile; alkyl (meth)acrylate such as methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; styrene;
Aromatic monomers such as α-methylstyrene and vinyltoluene; individual monomers such as α-olefins such as ethylene and propylene, vinyl compounds such as vinyl acetate and vinyl propionate, and diene compounds such as butadiene and isoprene. Alternatively, it can be obtained by polymerizing any combination.
【００２１】ポリエステル樹脂としては多塩基酸と多価
アルコールの重縮合反応で得られる一般のポリエステル
樹脂で、多塩基酸としては例えばシュウ酸、コハク酸、
無水コハク酸、アジピン酸等の２塩基酸；フタル酸、無
水フタル酸、テレフタル酸、ヘキサヒドロフタル酸、ヘ
キサヒドロ無水フタル酸、トリメット酸等の芳香族脂肪
酸；マレイン酸、無水マレイン酸、フマール酸等の不飽
和２塩基酸等が、多価アルコールとしては例えばエチレ
ングリコール、プロピレングリコール、１，６−ヘキサ
ンジオール、ジエチレングリコール、トリエチレングリ
コール等のグリコール；ビスフェノールジヒドロキシプ
ロピルエーテル、水素化ビスフェノールＡ、グリセリン
、トリメチロールプロパン、ペンタエリスリトール等が
適宜使用される。The polyester resin is a general polyester resin obtained by a polycondensation reaction of a polybasic acid and a polyhydric alcohol, and examples of the polybasic acid include oxalic acid, succinic acid,
Dibasic acids such as succinic anhydride and adipic acid; Aromatic fatty acids such as phthalic acid, terephthalic acid, hexahydrophthalic acid, hexahydrophthalic anhydride, and trimetic acid; Maleic acid, maleic anhydride, fumaric acid, etc. Examples of polyhydric alcohols include glycols such as ethylene glycol, propylene glycol, 1,6-hexanediol, diethylene glycol, and triethylene glycol; bisphenol dihydroxypropyl ether, hydrogenated bisphenol A, glycerin, and triethylene glycol; Methylolpropane, pentaerythritol, etc. are used as appropriate.
【００２２】アルキド樹脂としては、上記ポリエステル
を脂肪酸及び乾性油等でエステル化変性したものであり
、エポキシ変性、ロジン変性、フェノール樹脂変性のも
のがある。アクリル変性ポリエステル及びアクリル変性
アルキド樹脂としては、上記したポリエステル樹脂また
はアルキド樹脂中にアクリル重合体セグメントを組み込
んだ樹脂があげられる。上記した水性樹脂は各種樹脂の
１種あるいは２種以上を適宜使用することができる。
塗料用組成物とするための媒体としては、通常水が用い
られるが、さらに親水性の極性有機溶媒も、最大９０％
程度まで水媒体中に共存せしめることもできる。かかる
極性有機溶媒としては、例えばエチレングリコールモノ
メチルエーテル、エチレングリコールモノエチルエーテ
ル、メタノール、エタノールイソプロピルアルコール、
ｎ−ブタノール、Ｎ，Ｎ−ジメチルホルムアミド等が好
ましいものとしてあげられる。The alkyd resin is one obtained by esterifying and modifying the above polyester with a fatty acid, a drying oil, etc., and includes those modified with epoxy, rosin, and phenol resin. Examples of the acrylic-modified polyester and acrylic-modified alkyd resin include resins in which acrylic polymer segments are incorporated into the above-mentioned polyester resin or alkyd resin. As the aqueous resin described above, one type or two or more types of various resins can be used as appropriate. Water is usually used as a medium for forming coating compositions, but hydrophilic polar organic solvents can also be used in up to 90%
They can also coexist in an aqueous medium to some extent. Examples of such polar organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methanol, ethanol isopropyl alcohol,
Preferred examples include n-butanol and N,N-dimethylformamide.
【００２３】上記したグラフト共重合体と水性樹脂及び
水媒体との割合は塗装方法に合わせて任意の割合に調製
できるが、通常、水性樹脂３０〜８０重量％、水媒体７
０〜２０重量％、及びグラフト共重合体は水性樹脂に対
して、１〜３０重量である。また、エマルション系塗料
と異なりゲル粒子による構造粘性を持たせているわけで
はないので固形分を高めたハイソリッドなものにするこ
とも可能である。本発明の該グラフト共重合体使用して
得られる、顔料含有塗料組成物は、通常塗料に使用せら
れる任意の顔料を、上記グラフト共重合体を含有してな
る塗料用組成物に分散することにより調製される。使用
される顔料としては、特に制限はないが、雲母状酸化鉄
、ヒドロキシ炭酸鉛、四酸化三鉛、クロム酸鉛、硫化第
二水銀、ナトリウム−アルミノシリケート、フェロシア
ン化第二鉄、酸化コバルト、二酸化チタン、真珠光沢顔
料、ストロンチウムクロメート、チタニウム、チタンブ
ラック、ジンククロメート、四酸化三鉄、モリブデンレ
ッド、モリブデンホワイト、一酸化鉛、リトポン等の無
機顔料；ファストエロー、ジスアゾエロー、ジスアゾオ
レンジ、ナフトールレッド等の水不溶性アゾ顔料類；レ
ーキレッドＣ、カーミン６Ｂ、パーマネントレッド２Ｂ
等の水溶性アゾ顔料類及びフタロシアニンブルー、イソ
インドリン、キナクリドン、ジオキサジンバイオレット
、ペリノン・ペリレン等の有機顔料等が好ましいものと
して挙げられる。塗料用組成物中に分散させる顔料は、
塗料用組成物に対して、０．５〜５０重量％程度である
。顔料の配合方法は、予め水性樹脂の一部を用いて顔料
ペーストを調製し、これにグラフト共重合体、残りの水
性樹脂、その他の添加剤を加え、公知のペイントシェイ
カー、ゲートミキサー、高速ディスパー等の分散機械を
使用して均一に混合分散するのが好ましい。しかしなが
ら、各成分を分散機械により混合分散して塗料化するこ
とも可能である。The ratio of the above graft copolymer to the aqueous resin and aqueous medium can be adjusted to any desired ratio depending on the coating method, but usually 30 to 80% by weight of the aqueous resin and 7% by weight of the aqueous medium.
0 to 20% by weight, and 1 to 30% by weight of the graft copolymer based on the aqueous resin. Furthermore, unlike emulsion-based paints, it does not have structural viscosity due to gel particles, so it is possible to make it high solid with an increased solid content. The pigment-containing coating composition obtained by using the graft copolymer of the present invention can be obtained by dispersing any pigment commonly used in coatings into a coating composition containing the graft copolymer. Prepared by The pigments used are not particularly limited, but include micaceous iron oxide, lead hydroxy carbonate, trilead tetroxide, lead chromate, mercuric sulfide, sodium-aluminosilicate, ferric ferrocyanide, and cobalt oxide. , titanium dioxide, pearlescent pigments, strontium chromate, titanium, titanium black, zinc chromate, triiron tetroxide, molybdenum red, molybdenum white, lead monoxide, lithopone, and other inorganic pigments; fast yellow, disazo yellow, disazo orange, naphthol red Water-insoluble azo pigments such as Lake Red C, Carmine 6B, Permanent Red 2B
Preferred examples include water-soluble azo pigments such as phthalocyanine blue, isoindoline, quinacridone, dioxazine violet, perinone/perylene, and the like. The pigment to be dispersed in the coating composition is
The amount is about 0.5 to 50% by weight based on the coating composition. The method for blending pigments is to prepare a pigment paste in advance using a portion of the water-based resin, add the graft copolymer, the remaining water-based resin, and other additives, and then use a known paint shaker, gate mixer, or high-speed disperser. It is preferable to uniformly mix and disperse using a dispersion machine such as . However, it is also possible to mix and disperse each component using a dispersion machine to form a paint.
【００２４】本発明の塗料用組成物並びに顔料含有塗料
用組成物に対しては、所望により架橋剤を添加すること
ができる。例えばメラミンホルムアルデヒド樹脂、尿素
樹脂、メトキシ変性、ブトキシ変性メラミンホルムアル
デヒド樹脂、グアナミン樹脂等のアミノプラスト、イソ
シアネート、ポリシオシアネート等のイソシアネート化
合物、フェノール樹脂等の公知の架橋剤が最大５０％程
度まで使用される。また、所望により垂れ防止剤、沈降
防止剤、はじき防止剤、色分れ防止剤、表面張力調製剤
、酸化防止剤、光安定化剤、紫外線吸収剤等の添加剤を
適宜、通常最大５％程度まで加えることも可能である。
これら架橋剤及び添加剤の使用量、配合方法は通常の塗
料製造に準じて適宜選択使用される。A crosslinking agent may be added to the coating composition and the pigment-containing coating composition of the present invention, if desired. For example, a known crosslinking agent such as melamine formaldehyde resin, urea resin, methoxy-modified or butoxy-modified melamine formaldehyde resin, aminoplast such as guanamine resin, isocyanate, isocyanate compound such as polycyocyanate, or phenol resin is used up to about 50%. Ru. Additionally, if desired, additives such as anti-sagging agents, anti-settling agents, anti-repelling agents, anti-color separation agents, surface tension adjusting agents, antioxidants, light stabilizers, ultraviolet absorbers, etc. may be added as appropriate, usually at a maximum of 5%. It is also possible to add to a certain extent. The amounts and blending methods of these crosslinking agents and additives are appropriately selected and used in accordance with ordinary paint manufacturing.
【００２５】本発明の塗料用組成物及び顔料含有塗料用
組成物は、そのままあるいは水で更に希釈し、スプレー
、浸漬、刷毛塗り等の通常の塗装方法により適用され乾
燥及び加熱による焼付けが行われて塗膜が得られる。
該塗料用組成物及び顔料含有塗料用組成物は界面活性剤
を含有せず、水不溶化ができることから、高光沢、耐久
性、耐水性の優れた塗面が得られる。なお、平滑性もす
ぐれた塗膜が得られる。また、本塗料用組成物及び顔料
含有塗料用組成物はハイソリッド化が可能であるので、
ハイソリッド化により焼付け時のプレヒートの必要がな
いのも注目すべき特徴である。更にグラフトする単量体
を適宜選択することにより、共重合体の機能を奏さしめ
て、界面活性を利用した効果的な表面修飾による表面性
状の改善、及び第三成分を混合する場合のブレンドの相
溶性の向上、並びに分散性の向上の効果をも有している
。The coating composition and the pigment-containing coating composition of the present invention can be applied as is or further diluted with water by a conventional coating method such as spraying, dipping, or brushing, and then dried and baked by heating. A coating film is obtained. Since the coating composition and the pigment-containing coating composition do not contain a surfactant and can be made water insoluble, a coated surface with high gloss, durability, and excellent water resistance can be obtained. Additionally, a coating film with excellent smoothness can be obtained. In addition, since the present coating composition and pigment-containing coating composition can be made into high solids,
Another notable feature is that, due to its high solidity, there is no need for preheating during baking. Furthermore, by appropriately selecting the monomers to be grafted, the functions of the copolymer can be activated, and the surface properties can be improved through effective surface modification using surface activity, and the phase of the blend can be improved when a third component is mixed. It also has the effect of improving solubility and dispersibility.
【００２６】[0026]
【実施例】以下、実施例により本発明を具体的に説明す
るが、本発明の実施の態様はこれにより限定されるもの
ではない。ここで、グラフト共重合体のグラフト率及び
グラフト効率を各々Ｇｒ（％）及びＥＧｒ（％）とする
と、以下の実施例に示したグラフト共重合によって得ら
れたグラフト共重合体のＧｒ（％）及びＥＧｒ（％）は
Ｎ−置換（メタ）アクリルアミド誘導体の重合体の重量
をＢ（ｇ）、得られたグラフト共重合体の重量をＧ（ｇ
）、グラフト共重合により副生したラジカル重合可能な
単量体の重合体の重量をＭ（ｇ）とするとＧｒ（％）は
下記式（１）に、ＥＧｒ（％）は下記式（２）に基づき
重量法により求めた。[Examples] The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Here, if the grafting rate and grafting efficiency of the graft copolymer are Gr (%) and EGr (%), respectively, then the Gr (%) of the graft copolymer obtained by the graft copolymerization shown in the following example and EGr (%), the weight of the polymer of N-substituted (meth)acrylamide derivative is B (g), and the weight of the obtained graft copolymer is G (g).
), and when the weight of the polymer of the radically polymerizable monomer by-produced by graft copolymerization is M (g), Gr (%) is expressed by the following formula (1), and EGr (%) is expressed by the following formula (2). It was determined by the gravimetric method based on the following.
【００２７】[0027]
【００２８】実施例１
Ｎ−アクリロイルピロリジン重合体０．５ｇを１，４−
ジオキサン２０ｍｌに溶解した後、スチレン１．０ｇ、
ベンゾイルパーオキサイド０．００７ｇを溶解させ、６
０℃に昇温させ２４時間放置して重合を行った。重合終
了後、エーテル中に沈澱させ沈澱物を濾過してシクロヘ
キサンで抽出を行いスチレンをグラフトさせたＮ−アク
リロイルピロリジン共重合体を得た。この時のグラフト
率は１２．０％で、グラフト効率は２７．７％であった
。Example 1 0.5 g of N-acryloylpyrrolidine polymer was added to 1,4-
After dissolving in 20 ml of dioxane, 1.0 g of styrene,
Dissolve 0.007g of benzoyl peroxide, 6
The temperature was raised to 0° C. and polymerization was carried out by standing for 24 hours. After the polymerization was completed, the mixture was precipitated in ether, the precipitate was filtered, and extracted with cyclohexane to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. The grafting rate at this time was 12.0%, and the grafting efficiency was 27.7%.
【００２９】実施例２
Ｎ−アクリロイルピロリジン重合体０．５ｇをベンゼン
２０ｍｌに溶解した後、スチレン１．０ｇ、ベンゾイル
パーオキサイド０．００７ｇを溶解させ、８０℃に昇温
させ２４時間放置して重合を行った。重合終了後、エー
テル中に注ぎ重合物を沈澱させ沈澱物を濾過してシクロ
ヘキサンで抽出を行いスチレンをグラフトさせたＮ−ア
クリロイルピロリジン共重合体を得た。この時のグラフ
ト率は１６．９％で、グラフト効率は１８．２％であっ
た。Example 2 After dissolving 0.5 g of N-acryloylpyrrolidine polymer in 20 ml of benzene, 1.0 g of styrene and 0.007 g of benzoyl peroxide were dissolved, and the temperature was raised to 80° C. and left for 24 hours to polymerize. I did it. After the polymerization was completed, the polymer was poured into ether to precipitate it, and the precipitate was filtered and extracted with cyclohexane to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. The grafting rate at this time was 16.9%, and the grafting efficiency was 18.2%.
【００３０】実施例３
ベンゾイルパーオキサイド０．０３０ｇを使用した他は
すべて実施例２に準じてグラフト共重合を行いスチレン
をグラフトさせたＮ−アクリロイルピロリジン共重合体
を得た。この時のグラフト率は２９．７％で、グラフト
効率は１８．６％であった。Example 3 Graft copolymerization was carried out in the same manner as in Example 2 except that 0.030 g of benzoyl peroxide was used to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. The grafting rate at this time was 29.7%, and the grafting efficiency was 18.6%.
【００３１】実施例４
Ｎ−アクリロイルピロリジン重合体０．１３ｇを純水５
ｍｌに溶解した後、スチレン０．１３ｇ、ベンゾイルパ
ーオキサイド０．０１０ｇを添加してよく撹拌を行い、
４５℃に昇温させ２４時間放置して重合を行った。重合
終了後、重合溶液を凍結乾燥させた後、ベンゼンに溶解
させた。このベンゼン溶液をエーテル中に注ぎ重合物沈
澱させ沈澱物を濾過してシクロヘキサンで抽出を行いス
チレンをグラフトさせたＮ−アクリロイルピロリジン共
重合体を得た。この時のグラフト率は６．３％で、グラ
フト効率は３４．３％であった。Example 4 0.13 g of N-acryloylpyrrolidine polymer was added to 5 ml of pure water.
ml, add 0.13 g of styrene and 0.010 g of benzoyl peroxide and stir well.
The temperature was raised to 45° C. and polymerization was carried out by standing for 24 hours. After the polymerization was completed, the polymerization solution was freeze-dried and then dissolved in benzene. This benzene solution was poured into ether to precipitate a polymer, and the precipitate was filtered and extracted with cyclohexane to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. The grafting rate at this time was 6.3%, and the grafting efficiency was 34.3%.
【００３２】実施例５
ベンゾイルパーオキサイド０．０５０ｇを使用した他は
すべて実施例４に準じてグラフト共重合を行いスチレン
をグラフトさせたＮ−アクリロイルピロリジン共重合体
を得た。この時のグラフト率は２３．２％で、グラフト
効率は４３．５％であった。Example 5 Graft copolymerization was carried out in the same manner as in Example 4 except that 0.050 g of benzoyl peroxide was used to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. The grafting rate at this time was 23.2%, and the grafting efficiency was 43.5%.
【００３３】実施例６
Ｎ−アクリロイルピロリジン重合体０．１３ｇを純水５
ｍｌに溶解した後、スチレン０．１３ｇ、過硫酸カリウ
ム０．００５ｇを添加してよく撹拌を行い、４０℃に昇
温させ２４時間放置して重合を行った。重合終了後、重
合溶液を凍結乾燥させた後、ベンゼンに溶解させた。こ
のベンゼン溶液をエーテル中に注ぎ重合物を沈澱させ沈
澱物を濾過してシクロヘキサンで抽出を行いスチレンを
グラフトさせたＮ−アクリロイルピロリジン共重合体を
得た。この時のグラフト率は７６．６％で、グラフト効
率は７５．１％であった。Example 6 0.13 g of N-acryloylpyrrolidine polymer was added to 5 ml of pure water.
ml, 0.13 g of styrene and 0.005 g of potassium persulfate were added, stirred well, heated to 40° C., and left to stand for 24 hours to perform polymerization. After the polymerization was completed, the polymerization solution was freeze-dried and then dissolved in benzene. This benzene solution was poured into ether to precipitate a polymer, and the precipitate was filtered and extracted with cyclohexane to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. The grafting rate at this time was 76.6%, and the grafting efficiency was 75.1%.
【００３４】実施例７
過硫酸カリウム０．０１０ｇを使用した他はすべて実施
例６に準じてグラフト共重合を行いスチレンをグラフト
させたＮ−アクリロイルピロリジン共重合体を得た。こ
のものは水溶液中でエマルションを形成していた。この
時のグラフト率は９０．２％で、グラフト効率は８３．
４％であった。Example 7 Graft copolymerization was carried out in accordance with Example 6 except that 0.010 g of potassium persulfate was used to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. This product formed an emulsion in an aqueous solution. The grafting rate at this time was 90.2%, and the grafting efficiency was 83.
It was 4%.
【００３５】実施例８
スチレン０．２５ｇ、過硫酸カリウム０．００２５ｇを
使用した他はすべて実施例６に準じてグラフト共重合を
行いスチレンをグラフトさせたＮ−アクリロイルピロリ
ジン共重合体を得た。この時のグラフト率は１７７．０
％で、グラフト効率は９０．３％であった。以上実施例
１〜８から、有機溶媒中において、重合開始剤の量と有
機溶媒の種類等を変化させ、過酸化物系重合開始剤を用
いることにより、グラフト率１０〜３０％程度、グラフ
ト効率１５〜３０％程度のグラフト共重合体が容易に得
られ、水媒体中において水溶性の過酸化物系重合開始剤
の量と種類を変えて用いるこことにより、グラフト率、
７５〜１８０％程度、グラフト効率７５〜９０％程度の
グラフト共重合体を得ることかできることが分かる。Example 8 Graft copolymerization was carried out in the same manner as in Example 6 except that 0.25 g of styrene and 0.0025 g of potassium persulfate were used to obtain a styrene-grafted N-acryloylpyrrolidine copolymer. The grafting rate at this time was 177.0
%, the grafting efficiency was 90.3%. From the above Examples 1 to 8, by changing the amount of polymerization initiator and the type of organic solvent in the organic solvent, and using a peroxide-based polymerization initiator, the grafting efficiency was about 10 to 30%. A graft copolymer of about 15 to 30% can be easily obtained, and by varying the amount and type of water-soluble peroxide polymerization initiator in an aqueous medium, the grafting rate,
It can be seen that a graft copolymer having a graft efficiency of about 75 to 180% and a graft efficiency of about 75 to 90% can be obtained.
【００３６】実施例９
Ｎ−アクリロイルピロリジン重合体０．５ｇをベンゼン
２０ｍｌに溶解した後、メチルメタクリレート１．０ｇ
、ベンゾイルパーオキサイド０．０３０ｇを溶解させ、
８０℃に昇温させ２４時間放置して重合を行った。
重合終了後、エーテル中に注ぎ重合物を沈澱させ沈澱物
を濾過してシクロヘキサンで抽出を行いメチルメタクリ
レートをグラフトさせたＮ−アクリロイルピロリジン共
重合体を得た。この時のグラフト率は２１．４％で、グ
ラフト効率は１７．４％であった。Example 9 After dissolving 0.5 g of N-acryloylpyrrolidine polymer in 20 ml of benzene, 1.0 g of methyl methacrylate was dissolved.
, dissolve 0.030 g of benzoyl peroxide,
The temperature was raised to 80° C. and polymerization was carried out by standing for 24 hours. After the polymerization was completed, the polymer was poured into ether to precipitate it, and the precipitate was filtered and extracted with cyclohexane to obtain an N-acryloylpyrrolidine copolymer grafted with methyl methacrylate. The grafting rate at this time was 21.4%, and the grafting efficiency was 17.4%.
【００３７】実施例１０
Ｎ−アクリロイルピペリジン重合体０．５ｇをベンゼン
２０ｍｌに溶解した後、メチルメタクリレート１．０ｇ
、ベンゾイルパーオキサイド０．０３０ｇを溶解させ、
８０℃に昇温させ２４時間放置して重合を行った。
重合終了後、エーテル中に注ぎ重合物を沈澱させ沈澱物
を濾過してシクロヘキサンで抽出を行いメチルメタクリ
レートをグラフトさせたＮ−アクリロイルピペリジン共
重合体を得た。この時のグラフト率は１９．６％で、グ
ラフト効率は２１．６％であった。Example 10 After dissolving 0.5 g of N-acryloylpiperidine polymer in 20 ml of benzene, 1.0 g of methyl methacrylate was dissolved.
, dissolve 0.030 g of benzoyl peroxide,
The temperature was raised to 80° C. and polymerization was carried out by standing for 24 hours. After the polymerization was completed, the polymer was poured into ether to precipitate it, and the precipitate was filtered and extracted with cyclohexane to obtain an N-acryloylpiperidine copolymer grafted with methyl methacrylate. The grafting rate at this time was 19.6%, and the grafting efficiency was 21.6%.
【００３８】実施例１１
Ｎ−ｎ−プロピルアクリルアミド重合体０．５ｇをベン
ゼン２０ｍｌに溶解した後、アクリロニトリル１．０ｇ
、ベンゾイルパーオキサイド０．０３０ｇを溶解させ、
８０℃に昇温させ２４時間放置して重合を行った。
重合終了後、エーテル中に注ぎ重合物を沈澱させ沈澱物
を濾過してシクロヘキサンで抽出を行いアクリロニトリ
ルをグラフトさせたＮ−ｎ−プロピルアクリルアミド共
重合体を得た。この時のグラフト率は１８．５％で、グ
ラフト効率は１８．９％であった。Example 11 After dissolving 0.5 g of N-n-propylacrylamide polymer in 20 ml of benzene, 1.0 g of acrylonitrile was dissolved.
, dissolve 0.030 g of benzoyl peroxide,
The temperature was raised to 80° C. and polymerization was carried out by standing for 24 hours. After the polymerization was completed, the polymer was poured into ether to precipitate it, and the precipitate was filtered and extracted with cyclohexane to obtain an acrylonitrile-grafted N-n-propylacrylamide copolymer. The grafting rate at this time was 18.5%, and the grafting efficiency was 18.9%.
【００３９】実施例１２
Ｎ−イソプロピルアクリルアミド重合体０．５ｇをベン
ゼン２０ｍｌに溶解した後、酢酸ビニル１．０ｇ、ベン
ゾイルパーオキサイド０．０３０ｇを溶解させ、８０℃
に昇温させ２４時間放置して重合を行った。重合終了後
、エーテル中に注ぎ重合物を沈澱させ沈澱物を濾過して
シクロヘキサンで抽出を行い酢酸ビニルをグラフトさせ
たＮ−イソプロピルアクリルアミド共重合体を得た。
この時のグラフト率は１８．７％で、グラフト効率は１
９．４％であった。Example 12 After dissolving 0.5 g of N-isopropylacrylamide polymer in 20 ml of benzene, 1.0 g of vinyl acetate and 0.030 g of benzoyl peroxide were dissolved, and the mixture was heated at 80°C.
Polymerization was carried out by raising the temperature to 24 hours and leaving it for 24 hours. After the polymerization was completed, the polymer was poured into ether to precipitate it, and the precipitate was filtered and extracted with cyclohexane to obtain an N-isopropylacrylamide copolymer grafted with vinyl acetate. The grafting rate at this time was 18.7%, and the grafting efficiency was 1.
It was 9.4%.
【００４０】実施例１３〜１４
実施例９〜１２から、Ｎ−置換（メタ）アクリルアミド
系重合体の種類を変えたものに、グラフト重合可能な単
量体の種類を変えることにより、グラフト率１８〜２２
％程度、グラフト効率１７〜２２％程度で容易にグラフ
ト共重合することが可能であることがわかる。Examples 13 to 14 From Examples 9 to 12, a graft ratio of 18 ~22
It can be seen that graft copolymerization can be easily carried out with a graft efficiency of about 17 to 22%.
【００４１】〔水性樹脂の製造〕撹拌機、温度計、冷却
管を備えた５ｌの反応器にエチレングリコールモノブチ
ルエーテル３００ｇを仕込み、撹拌下１００℃に昇温し
た。ここにスチレン１５０ｇ、メチルメタクリレート２
００ｇ、ｎ−ブチルメタクリレート４００ｇ、２−ヒド
ロキシメタクリレート１６０ｇ、メタクリル酸９０ｇ、
アゾビスイソブチロニトリル４０ｇよりなる単量体を５
時間にわたり滴下して、更に３時間同温度で保持した後
、ジメチルエタノールアミン１００ｇと純水００ｇを添
加し、固形分５０％、数平均分子量５０００のアクリル
樹脂を得た。[Production of aqueous resin] 300 g of ethylene glycol monobutyl ether was charged into a 5-liter reactor equipped with a stirrer, a thermometer, and a cooling tube, and the temperature was raised to 100° C. while stirring. Here, 150 g of styrene, 2 methyl methacrylate
00g, n-butyl methacrylate 400g, 2-hydroxy methacrylate 160g, methacrylic acid 90g,
5 monomers consisting of 40 g of azobisisobutyronitrile
After dropping the mixture over a period of time and maintaining the same temperature for an additional 3 hours, 100 g of dimethylethanolamine and 00 g of pure water were added to obtain an acrylic resin with a solid content of 50% and a number average molecular weight of 5,000.
【００４２】〔塗料調製〕塗料配合を下記のように行っ
た。上記で得られたアクリル樹脂６０７ｇ、二酸化チタ
ン ＣＲ−９０（石原産業（株））５２０ｇをペイン
トシェイカーにより１時間顔料を分散した。更にサイメ
ルＣ−３５（メラミン樹脂、三井サイアナミッド（株）
、固形分１００％）１３０ｇ及び実施例８で得られたグ
ラフト共重合体を表１に示す量を加え、純水にて希釈し
Ｆｏｒｄ Ｃｕｐ＃４にて３０秒／２０℃に調製した
。[Paint Preparation] The paint was formulated as follows. Pigment was dispersed in 607 g of the acrylic resin obtained above and 520 g of titanium dioxide CR-90 (Ishihara Sangyo Co., Ltd.) using a paint shaker for 1 hour. Furthermore, Cymel C-35 (melamine resin, Mitsui Cyanamid Co., Ltd.)
, solid content 100%) and the graft copolymer obtained in Example 8 in the amounts shown in Table 1 were added, diluted with pure water, and prepared in a Ford Cup #4 at 30 seconds/20°C.
【００４３】〔塗装〕鋼板に調製した塗料をスプレー塗
装し、１０分間放置した後、１５０℃，３０分間焼き付
けて塗膜を得た。塗膜評価結果を表１に示す。[Painting] A steel plate was spray-coated with the prepared paint, left to stand for 10 minutes, and then baked at 150° C. for 30 minutes to obtain a coating film. The coating film evaluation results are shown in Table 1.
【００４４】比較例１
実施例１３〜１４の塗料調製においてグラフト共重合体
を無添加で調製した以外はすべて実施例１４〜１５に準
じて塗料を調製し、塗装を行い塗膜を得た。塗膜評価結
果を表１に示す。Comparative Example 1 A coating material was prepared in the same manner as in Examples 14 to 15 except that no graft copolymer was added in the preparation of the coating material in Examples 13 to 14, and coating was performed to obtain a coating film. The coating film evaluation results are shown in Table 1.
【００４５】[0045]
【表１】
１）顔料分散性；ガラス板上に塗膜を形成し、顔料の分
散状態を目視判定した。分散状態が良好なもの◎、不良
なもの×とした。
２）耐水性；ガラス板状に塗膜を形成した後、４０℃の
水に３日間浸透させた時の塗膜の状態を黙視判定した。
塗膜状態が良好なもの◎、膨れ、白化等が生じたもの×
とした。[Table 1] 1) Pigment dispersibility: A coating film was formed on a glass plate, and the dispersion state of the pigment was visually judged. Those with good dispersion state were rated ◎, and those with poor dispersion state were rated ×. 2) Water resistance: After forming a coating film on a glass plate, the coating film was soaked in water at 40° C. for 3 days, and the condition of the coating film was visually evaluated. Those with good paint film condition◎, those with blistering, whitening, etc.×
And so.
【００４６】[0046]
【発明の効果】（１）本発明のグラフト共重合体は、グ
ラフト重合する単量体として水不溶性のものを選択する
ことにより、特定のＮ−置換（メタ）アクリルアミド系
重合体の性質を維持したまま不溶化することが可能であ
る。
（２）感温性を利用した水の分離、溶質の透過制御膜、
吸着分離樹脂及び膜、水蒸気の吸収・放出、防曇樹脂等
へ応用することが出来る。
（３）本発明のグラフト共重合体は、単量体の種類の選
択により、各種材料との相溶性が高いので樹脂の相溶化
剤となることが期待できる。
（４）本発明の塗料組成物及び顔料分散剤を塗装し、焼
付けすることにより高光沢、耐久性、耐水性の優れた塗
膜が得られる。Effects of the Invention (1) The graft copolymer of the present invention maintains the properties of a specific N-substituted (meth)acrylamide polymer by selecting a water-insoluble monomer for graft polymerization. It is possible to make it insolubilized while it remains. (2) Water separation and solute permeation control membrane using temperature sensitivity,
It can be applied to adsorption separation resins and membranes, water vapor absorption and release, antifogging resins, etc. (3) The graft copolymer of the present invention has high compatibility with various materials depending on the selection of the type of monomer, so it can be expected to serve as a compatibilizer for resins. (4) By coating and baking the coating composition and pigment dispersant of the present invention, a coating film with high gloss, durability, and excellent water resistance can be obtained.
Claims (4)
表される 【化１】 【化２】 Ｎ−置換（メタ）アクリルアミド誘導体を重合してなる
Ｎ−置換（メタ）アクリルアミド系重合体に、ラジカル
重合可能な単量体をグラフト共重合せしめてなるグラフ
ト共重合体。Claim 1: An N-substituted (meth)acrylamide polymer obtained by polymerizing an N-substituted (meth)acrylamide derivative represented by general formula (I) or general formula (II) [Chemical 1] [Chemical 2] A graft copolymer made by graft copolymerizing a monomer that can be radically polymerized.
１記載のＮ−置換（メタ）アクリルアミド系重合体にラ
ジカル重合可能な単量体をグラフト共重合せしめるグラ
フト共重合体の製造方法。2. A method for producing a graft copolymer, which comprises graft copolymerizing a radically polymerizable monomer to the N-substituted (meth)acrylamide polymer according to claim 1 in the presence of a peroxide polymerization initiator. .
有してなる塗料用組成物。3. A coating composition comprising the graft copolymer according to claim 1.
を分散せしめてなる顔料含有塗料用組成物。4. A pigment-containing coating composition comprising a pigment dispersed in the coating composition according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12437391A JPH04351615A (en) | 1991-05-29 | 1991-05-29 | Graft copolymer and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12437391A JPH04351615A (en) | 1991-05-29 | 1991-05-29 | Graft copolymer and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04351615A true JPH04351615A (en) | 1992-12-07 |
Family
ID=14883796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12437391A Pending JPH04351615A (en) | 1991-05-29 | 1991-05-29 | Graft copolymer and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04351615A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023153273A1 (en) * | 2022-02-09 | 2023-08-17 | Jnc株式会社 | Draw solution, water treatment method, and water treatment apparatus |
| WO2024058248A1 (en) * | 2022-09-16 | 2024-03-21 | 株式会社日本触媒 | Draw solute, draw solution, and method for treating raw water |
-
1991
- 1991-05-29 JP JP12437391A patent/JPH04351615A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023153273A1 (en) * | 2022-02-09 | 2023-08-17 | Jnc株式会社 | Draw solution, water treatment method, and water treatment apparatus |
| WO2024058248A1 (en) * | 2022-09-16 | 2024-03-21 | 株式会社日本触媒 | Draw solute, draw solution, and method for treating raw water |
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