JP2013177573A - Water-soluble polymer pigment dispersant and aqueous composition containing water-soluble polymer pigment dispersant - Google Patents
Water-soluble polymer pigment dispersant and aqueous composition containing water-soluble polymer pigment dispersant Download PDFInfo
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- JP2013177573A JP2013177573A JP2013018026A JP2013018026A JP2013177573A JP 2013177573 A JP2013177573 A JP 2013177573A JP 2013018026 A JP2013018026 A JP 2013018026A JP 2013018026 A JP2013018026 A JP 2013018026A JP 2013177573 A JP2013177573 A JP 2013177573A
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- parts
- water
- weight
- soluble polymer
- pigment dispersant
- Prior art date
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- 239000000049 pigment Substances 0.000 title claims abstract description 150
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 128
- 229920003169 water-soluble polymer Polymers 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims description 41
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 229920001577 copolymer Polymers 0.000 claims abstract description 72
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 5
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims abstract 2
- 239000007864 aqueous solution Substances 0.000 claims description 57
- -1 alkali metal salt Chemical class 0.000 claims description 35
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 16
- 239000003973 paint Substances 0.000 abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 90
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 67
- 238000004519 manufacturing process Methods 0.000 description 48
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 38
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 28
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 25
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 25
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 22
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 21
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 20
- 238000001816 cooling Methods 0.000 description 19
- 238000005227 gel permeation chromatography Methods 0.000 description 18
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 15
- 239000012860 organic pigment Substances 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 239000012855 volatile organic compound Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 230000003472 neutralizing effect Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000004094 surface-active agent 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
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- XQBHAZDVLGNSOJ-UHFFFAOYSA-N 1-(4-ethenylphenyl)-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=C(C=C)C=C1 XQBHAZDVLGNSOJ-UHFFFAOYSA-N 0.000 description 2
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- CFZDMXAOSDDDRT-UHFFFAOYSA-N 4-ethenylmorpholine Chemical compound C=CN1CCOCC1 CFZDMXAOSDDDRT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- WTFXTQVDAKGDEY-UHFFFAOYSA-N (-)-chorismic acid Natural products OC1C=CC(C(O)=O)=CC1OC(=C)C(O)=O WTFXTQVDAKGDEY-UHFFFAOYSA-N 0.000 description 1
- ZOKCNEIWFQCSCM-UHFFFAOYSA-N (2-methyl-4-phenylpent-4-en-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)CC(=C)C1=CC=CC=C1 ZOKCNEIWFQCSCM-UHFFFAOYSA-N 0.000 description 1
- KEEKMOIRJUWKNK-CABZTGNLSA-N (2S)-2-[[2-[(4R)-4-(difluoromethyl)-2-oxo-1,3-thiazolidin-3-yl]-5,6-dihydroimidazo[1,2-d][1,4]benzoxazepin-9-yl]amino]propanamide Chemical compound FC([C@H]1N(C(SC1)=O)C=1N=C2N(CCOC3=C2C=CC(=C3)N[C@H](C(=O)N)C)C=1)F KEEKMOIRJUWKNK-CABZTGNLSA-N 0.000 description 1
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- NYNZQNWKBKUAII-KBXCAEBGSA-N (3s)-n-[5-[(2r)-2-(2,5-difluorophenyl)pyrrolidin-1-yl]pyrazolo[1,5-a]pyrimidin-3-yl]-3-hydroxypyrrolidine-1-carboxamide Chemical compound C1[C@@H](O)CCN1C(=O)NC1=C2N=C(N3[C@H](CCC3)C=3C(=CC=C(F)C=3)F)C=CN2N=C1 NYNZQNWKBKUAII-KBXCAEBGSA-N 0.000 description 1
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- HXQKJEIGFRLGIH-UHFFFAOYSA-N 1-ethenyl-2h-pyrazine Chemical compound C=CN1CC=NC=C1 HXQKJEIGFRLGIH-UHFFFAOYSA-N 0.000 description 1
- LNKDTZRRFHHCCV-UHFFFAOYSA-N 1-ethenyl-2h-pyrimidine Chemical compound C=CN1CN=CC=C1 LNKDTZRRFHHCCV-UHFFFAOYSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- DCRYNQTXGUTACA-UHFFFAOYSA-N 1-ethenylpiperazine Chemical compound C=CN1CCNCC1 DCRYNQTXGUTACA-UHFFFAOYSA-N 0.000 description 1
- PBGPBHYPCGDFEZ-UHFFFAOYSA-N 1-ethenylpiperidin-2-one Chemical compound C=CN1CCCCC1=O PBGPBHYPCGDFEZ-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- ZSDGHWLLLGYAJV-AHEHSYJASA-N 2-[(E)-[(E)-3-[1-(2-nitrophenyl)pyrrol-2-yl]prop-2-enylidene]amino]guanidine Chemical compound NC(N)=N\N=C\C=C\C1=CC=CN1C1=CC=CC=C1[N+]([O-])=O ZSDGHWLLLGYAJV-AHEHSYJASA-N 0.000 description 1
- SSORSZACHCNXSJ-UHFFFAOYSA-N 2-[2-(3,4-dichlorophenyl)-3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]imidazol-4-yl]acetonitrile Chemical compound ClC=1C=C(C=CC=1Cl)C=1N(C(=CN=1)CC#N)C1=NC(=NC=C1)NCC(C)O SSORSZACHCNXSJ-UHFFFAOYSA-N 0.000 description 1
- DILISPNYIVRDBP-UHFFFAOYSA-N 2-[3-[2-(2-hydroxypropylamino)pyrimidin-4-yl]-2-naphthalen-2-ylimidazol-4-yl]acetonitrile Chemical compound OC(CNC1=NC=CC(=N1)N1C(=NC=C1CC#N)C1=CC2=CC=CC=C2C=C1)C DILISPNYIVRDBP-UHFFFAOYSA-N 0.000 description 1
- LXCUAFVVTHZALS-UHFFFAOYSA-N 3-(3-methoxyphenyl)piperidine Chemical compound COC1=CC=CC(C2CNCCC2)=C1 LXCUAFVVTHZALS-UHFFFAOYSA-N 0.000 description 1
- NIAXWFTYAJQENP-UHFFFAOYSA-N 3-ethenyl-2h-1,3-oxazole Chemical compound C=CN1COC=C1 NIAXWFTYAJQENP-UHFFFAOYSA-N 0.000 description 1
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- RSIWALKZYXPAGW-NSHDSACASA-N 6-(3-fluorophenyl)-3-methyl-7-[(1s)-1-(7h-purin-6-ylamino)ethyl]-[1,3]thiazolo[3,2-a]pyrimidin-5-one Chemical compound C=1([C@@H](NC=2C=3N=CNC=3N=CN=2)C)N=C2SC=C(C)N2C(=O)C=1C1=CC=CC(F)=C1 RSIWALKZYXPAGW-NSHDSACASA-N 0.000 description 1
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- KYNSBQPICQTCGU-UHFFFAOYSA-N Benzopyrane Chemical compound C1=CC=C2C=CCOC2=C1 KYNSBQPICQTCGU-UHFFFAOYSA-N 0.000 description 1
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- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
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- 150000001346 alkyl aryl ethers Chemical group 0.000 description 1
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- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- AOLJCKIDPDZWBS-UHFFFAOYSA-N methyl 3-(dimethylamino)-2-methylprop-2-enoate Chemical compound COC(=O)C(C)=CN(C)C AOLJCKIDPDZWBS-UHFFFAOYSA-N 0.000 description 1
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- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229940110337 pigment blue 1 Drugs 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- RAJUSMULYYBNSJ-UHFFFAOYSA-N prop-1-ene-1-sulfonic acid Chemical compound CC=CS(O)(=O)=O RAJUSMULYYBNSJ-UHFFFAOYSA-N 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- OEBIHOVSAMBXIB-SJKOYZFVSA-N selitrectinib Chemical compound C[C@@H]1CCC2=NC=C(F)C=C2[C@H]2CCCN2C2=NC3=C(C=NN3C=C2)C(=O)N1 OEBIHOVSAMBXIB-SJKOYZFVSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 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
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 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
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Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
本発明は、水溶性高分子顔料分散剤及び水溶性高分子顔料分散剤を含有する水系組成物に関する。 The present invention relates to a water-soluble polymer pigment dispersant and an aqueous composition containing a water-soluble polymer pigment dispersant.
一般に、印刷インキ、塗料等の分野で用いられている顔料は、高い鮮明性を得るため顔料粒子を高度に微細化する必要がある。しかし、顔料をより微細化していくと、顔料粒子間の凝集力が強くなり、インキや塗料が高粘度を示す場合が多い。 In general, pigments used in the fields of printing inks, paints, and the like require highly fine pigment particles in order to obtain high sharpness. However, when the pigment is made finer, the cohesive force between the pigment particles becomes stronger, and the ink or paint often has a high viscosity.
これに対しては、顔料分散剤を使用し、顔料とビヒクル間の親和性を良くし、分散体の安定化を図ることが知られており、これまでに様々な顔料分散剤が開示されている。例えば、重合性オリゴマーにおける末端のエチレン性不飽和二重結合と窒素含有モノマーにおけるエチレン性不飽和結合との重合反応によって形成されるグラフト共重合体を含有する顔料分散剤等が挙げられる（特許文献１と２参照）。しかしながら、これらの顔料分散剤は、揮発性有機化合物（ＶＯＣ、Ｖｏｌａｔｉｌｅ Ｏｒｇａｎｉｃ Ｃｏｍｐｏｕｎｄｓ）を使用するため、顔料分散液には多くのＶＯＣが含まれることになる。これに対して一方で環境に配慮した低ＶＯＣ塗料やゼロＶＯＣ塗料が強く求められている。 For this, it is known to use a pigment dispersant to improve the affinity between the pigment and the vehicle and to stabilize the dispersion, and various pigment dispersants have been disclosed so far. Yes. For example, a pigment dispersant containing a graft copolymer formed by a polymerization reaction between a terminal ethylenically unsaturated double bond in a polymerizable oligomer and an ethylenically unsaturated bond in a nitrogen-containing monomer (Patent Document) 1 and 2). However, since these pigment dispersants use volatile organic compounds (VOC, Volatile Organic Compounds), the pigment dispersion contains a large amount of VOC. On the other hand, there is a strong demand for environmentally-friendly low VOC paint and zero VOC paint.
低ＶＯＣ塗料やゼロＶＯＣ塗料として使用可能な顔料分散剤として、水溶性の顔料分散剤が提案されている。具体的には、例えば、芳香族および／または複素環ビニルモノマーユニットと、酸基を有するモノマーユニットと、（メタ）アクリル酸エステルモノマーユニットと、数平均分子量が１５０〜１，５００のポリアルキレングリコール鎖または該グリコールのモノアルキルエーテル鎖を有するモノマーユニットとから構成される分散剤（特許文献３参照。）や所定の単量体、含窒素不飽和単量体及び不飽和カルボン酸の共重合体である分散剤（特許文献４参照）が提案されている。 A water-soluble pigment dispersant has been proposed as a pigment dispersant that can be used as a low VOC paint or a zero VOC paint. Specifically, for example, an aromatic and / or heterocyclic vinyl monomer unit, a monomer unit having an acid group, a (meth) acrylic acid ester monomer unit, and a polyalkylene glycol having a number average molecular weight of 150 to 1,500 A dispersant comprising a chain or a monomer unit having a monoalkyl ether chain of the glycol (see Patent Document 3), a predetermined monomer, a nitrogen-containing unsaturated monomer, and a copolymer of an unsaturated carboxylic acid A dispersant (see Patent Document 4) is proposed.
しかしながら、これらの水溶性の分散剤は、微細化した顔料に対する分散性能がまだ十分ではなかった。そのため、高度な分散性能を有しつつ、優れた粘度適性、及び貯蔵安定性をもつ低ＶＯＣ塗料に使用可能な水溶性顔料分散剤が望まれている。 However, these water-soluble dispersants have not yet been sufficiently dispersible with respect to finer pigments. Therefore, there is a demand for a water-soluble pigment dispersant that can be used for a low VOC paint having high viscosity performance and excellent viscosity suitability and storage stability.
本発明は、顔料に対する高い分散性、高い貯蔵安定性、適正な粘度範囲、良好な色調を有する水溶性高分子顔料分散剤及び水溶性高分子顔料分散剤を含有する水系組成物を提供することを目的とする。 The present invention provides a water-soluble polymer pigment dispersant having high dispersibility to pigments, high storage stability, an appropriate viscosity range, and a good color tone, and an aqueous composition containing the water-soluble polymer pigment dispersant. With the goal.
本発明者らは前記課題を解決すべく鋭意検討を重ねた結果、特定の４種類の単量体を必須構成成分として得られる共重合体を含む分散剤とすることにより、上記課題を解決できることを見出し、本発明を完成させた。 As a result of intensive studies to solve the above-mentioned problems, the present inventors can solve the above-mentioned problems by making a dispersant containing a copolymer obtained from four specific types of monomers as essential components. The present invention was completed.
すなわち、本発明１は、窒素原子を含むラジカル重合性単量体（Ａ）、炭素数１〜１０のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体（Ｂ）、α，β−不飽和ジカルボン酸（Ｃ）及び一般式（１）で表わされる単量体（Ｄ）を必須構成成分とする共重合体を含有する水溶性高分子顔料分散剤である。
また本発明２は、本発明１において上記共重合体の２５重量％溶液における粘度が１００〜２０００ｍＰａ・ｓである水溶性高分子顔料分散剤である。 In addition, the present invention 2 is a water-soluble polymer pigment dispersant having a viscosity of 100 to 2000 mPa · s in a 25 wt% solution of the above copolymer in the present invention 1.
また本発明３は、本発明１又は２において、上記共重合体の２５重量％溶液における色調が１ガードナー以下である水溶性高分子顔料分散剤である。 Invention 3 is the water-soluble polymer pigment dispersant according to Invention 1 or 2, wherein the color tone in a 25% by weight solution of the copolymer is 1 Gardner or less.
また本発明４は、本発明１〜３のいずれかにおいて、上記窒素原子を含むラジカル重合性単量体（Ａ）がアミド基を有する（メタ）アクリルモノマーである水溶性高分子顔料分散剤である。 Invention 4 is the water-soluble polymer pigment dispersant according to any one of Inventions 1 to 3, wherein the radical polymerizable monomer (A) containing a nitrogen atom is a (meth) acrylic monomer having an amide group. is there.
また本発明５は、本発明１〜４のいずれかにおいて、上記単量体（Ｄ）がアルカリ金属塩である水溶性高分子顔料分散剤である。 In addition, the present invention 5 is the water-soluble polymer pigment dispersant according to any one of the present invention 1 to 4, wherein the monomer (D) is an alkali metal salt.
また本発明６は、本発明１〜５のいずれかにおいて、上記（Ｄ）一般式（１）で表わされる単量体の共重合体における含有量が５〜１５重量％である水溶性高分子顔料分散剤である。 Moreover, this invention 6 is water-soluble polymer whose content in the copolymer of the monomer represented by the said (D) general formula (1) in any one of this invention 1-5 is 5 to 15 weight%. It is a pigment dispersant.
また本発明７は、本発明１〜６のいずれかにおいて、上記共重合体の重量平均分子量が７５００〜２００００である水溶性高分子顔料分散剤である。 In addition, the present invention 7 is the water-soluble polymer pigment dispersant according to any one of the present inventions 1 to 6, wherein the copolymer has a weight average molecular weight of 7500 to 20000.
また本発明８は、水性溶媒中に、本発明１〜７の水溶性高分子顔料分散剤と色素を含有する水系組成物である。 The present invention 8 is an aqueous composition containing the water-soluble polymer pigment dispersant of the present invention 1 to 7 and a dye in an aqueous solvent.
本発明の水溶性高分子顔料分散剤は、顔料に対する高い分散性、顔料分散液の高い貯蔵安定性、適正な粘度範囲、良好な色調を有する。また、本発明の水溶性高分子顔料分散剤を使用した顔料分散液は、低粘度を有し、顔料の添加量が増えても低粘度を維持することができる。更に、本発明の水溶性高分子顔料分散剤は、優れた分散性を有するため、低ＶＯＣである水溶性の塗料、印刷インキ、インクジェット用インキ等に用いることができる。 The water-soluble polymer pigment dispersant of the present invention has high dispersibility with respect to the pigment, high storage stability of the pigment dispersion, proper viscosity range, and good color tone. In addition, the pigment dispersion using the water-soluble polymer pigment dispersant of the present invention has a low viscosity, and can maintain a low viscosity even when the amount of the pigment added increases. Furthermore, since the water-soluble polymer pigment dispersant of the present invention has excellent dispersibility, it can be used for water-soluble paints, printing inks, ink-jet inks and the like having a low VOC.
本発明の水溶性高分子顔料分散剤は、水溶性、かつ、高分子の分散剤であり、色素の分散に使用するものである。 The water-soluble polymer pigment dispersant of the present invention is a water-soluble and polymer dispersant and is used for dispersing a dye.
本発明の水溶性高分子顔料分散剤の必須原料は、窒素原子を含むラジカル重合性単量体（Ａ）、炭素数１〜１０のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体（Ｂ）、α，β−不飽和ジカルボン酸（Ｃ）及び一般式（１）で表わされる単量体（Ｄ）である。
上記窒素原子を含むラジカル重合性単量体（Ａ）（以下、（Ａ）成分という）は、ラジカル重合性の不飽和結合を有する単量体であれば特に限定されない。顔料の分散剤の吸着性の点から好ましくは、アミド基を有する（メタ）アクリルモノマー、アミノ基を有する（メタ）アクリルモノマー、含窒素複素環式（メタ）アクリルモノマー、ビニル複素環式アミド、含窒素複素環式ビニルモノマー、含窒素芳香複素環式ビニルモノマー、アミノ基を有するビニルモノマー、アリルモノマーが挙げられる。具体例としては、アクリルアミド、メタクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ−エチル（メタ）アクリルアミド、Ｎ−（２‐ヒドロキシエチル）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド、Ｎ−ジメチルアミノブチル（メタ）アクリルアミド、Ｎ−ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ−ジメチルアミノエチル（メタ）アクリルアミドなどのアミド基を有する（メタ）アクリルモノマー；Ｎ，Ｎ−ジメチルアミノ（メタ）アクリル酸メチル、Ｎ，Ｎ−ジメチルアミノ（メタ）アクリル酸エチル、Ｎ，Ｎ−ジメチルアミノ（メタ）アクリル酸プロピル、Ｎ，Ｎ−ジメチルアミノ（メタ）アクリル酸ブチル、Ｎ，Ｎ−ジエチルアミノ（メタ）アクリル酸エチルなどのアミノ基を有する（メタ）アクリルモノマー；Ｎ−（２−メタクリロイルオキシエチル）エチレン尿素、Ｎ−（メタ）アクリロイルモルホリンなどの含窒素複素環式（メタ）アクリルモノマー；Ｎ−ビニル−２−ピロリドン、Ｎ−ビニルピペリドンなどのビニル複素環式アミド；Ｎ−ビニルモルホリン、Ｎ−ビニルカプロラクタム、Ｎ−ビニルピペラジンなどの含窒素複素環式ビニルモノマー；２−ビニルピリジン、３−ビニルピリジン、２−メチル−５−ビニルピリジン、３−エチル−４−ビニルピリジン、２，３−ジメチル−５−ビニルピリジン、Ｎ−ビニルピリミジン、Ｎ−ビニルイミダゾール、Ｎ−ビニルピラジン、Ｎ−ビニルオキサゾールなどの含窒素芳香複素環式ビニルモノマー；ジメチルアミノメチルスチレン、ジメチルアミノエチルスチレン、ビニルアミンなどのアミノ基を有するビニルモノマー、アリルモノマーが挙げられる。（Ａ）成分は、これらの１種又は２種以上を用いることができる。これらの中でも、顔料への分散剤の吸着性を考慮すると、アミド基を有する（メタ）アクリルモノマーが好ましく、中でも特にアクリルアミドおよび／またはメタクリルアミドが好ましい。 The radical polymerizable monomer (A) containing nitrogen atom (hereinafter referred to as component (A)) is not particularly limited as long as it is a monomer having a radical polymerizable unsaturated bond. From the viewpoint of the adsorptivity of the pigment dispersant, (meth) acrylic monomer having an amide group, (meth) acrylic monomer having amino group, nitrogen-containing heterocyclic (meth) acrylic monomer, vinyl heterocyclic amide, Examples thereof include a nitrogen-containing heterocyclic vinyl monomer, a nitrogen-containing aromatic heterocyclic vinyl monomer, a vinyl monomer having an amino group, and an allyl monomer. Specific examples include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N- (2-hydroxyethyl) acrylamide, N, N-dimethyl (meth) acrylamide, N-dimethylamino. (Meth) acrylic monomers having an amide group such as butyl (meth) acrylamide, N-dimethylaminopropyl (meth) acrylamide, N-dimethylaminoethyl (meth) acrylamide; methyl N, N-dimethylamino (meth) acrylate, N, N-dimethylamino (meth) acrylate ethyl, N, N-dimethylamino (meth) acrylate propyl, N, N-dimethylamino (meth) acrylate butyl, N, N-diethylamino (meth) acrylate ethyl (Meth) a having an amino group such as A nitrogen-containing heterocyclic (meth) acrylic monomer such as N- (2-methacryloyloxyethyl) ethyleneurea or N- (meth) acryloylmorpholine; a vinyl heterocyclic ring such as N-vinyl-2-pyrrolidone or N-vinylpiperidone Formula amides; nitrogen-containing heterocyclic vinyl monomers such as N-vinylmorpholine, N-vinylcaprolactam, N-vinylpiperazine; 2-vinylpyridine, 3-vinylpyridine, 2-methyl-5-vinylpyridine, 3-ethyl- Nitrogen-containing aromatic heterocyclic vinyl monomers such as 4-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, N-vinylpyrimidine, N-vinylimidazole, N-vinylpyrazine, N-vinyloxazole; dimethylaminomethylstyrene , Dimethylaminoethyl styrene, vinyl Vinyl monomers having an amino group such as down, allyl monomers. As the component (A), one or more of these may be used. Among these, considering the adsorptivity of the dispersant to the pigment, (meth) acrylic monomers having an amide group are preferable, and acrylamide and / or methacrylamide are particularly preferable.
上記炭素数１〜１０のアルキル基を有する（メタ）アクリル酸アルキルエステル単量体（Ｂ）（以下、（Ｂ）成分という）の具体例としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸Ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｓｅｃ−ブチル、（メタ）アクリル酸ｔｅｒｔ−ブチル、（メタ）アクリル酸Ｎ−オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸デシル、（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル等が挙げられる。（Ｂ）成分は、これらの１種又は２種以上を用いることができる。これらの中でも顔料への分散剤の吸着性及び水への分散性の観点から（メタ）アクリル酸２−エチルヘキシル、又は（メタ）アクリル酸２−エチルヘキシルと（メタ）アクリル酸シクロヘキシルの併用が好ましい。 Specific examples of the (meth) acrylic acid alkyl ester monomer (B) (hereinafter referred to as (B) component) having an alkyl group having 1 to 10 carbon atoms include methyl (meth) acrylate and (meth) acrylic. Ethyl acetate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, N-octyl (meth) acrylate, (meth) acryl Examples include 2-ethylhexyl acid, decyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. As the component (B), one or more of these can be used. Among these, from the viewpoint of the adsorptivity of the dispersant to the pigment and the dispersibility in water, 2-ethylhexyl (meth) acrylate, or a combination of 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate is preferable.
上記α，β−不飽和ジカルボン酸（Ｃ）（以下、（Ｃ）成分という）は、不飽和結合を有し、２つのカルボキシル基を有するものであれば、特に限定されない。具体例としては、例えば、炭素数が４のマレイン酸、無水マレイン酸、フマル酸、炭素数が５のイタコン酸、シトラコン酸、メサコン酸、炭素数が１０のコリスミ酸等が挙げられる。また、（Ｃ）成分のカルボキシル基を塩基によって一部又はすべて中和しても良い。具体的な塩基の例として、水酸化ナトリウム、水酸化カリウム、アンモニア等が挙げられる。（Ｃ）成分により、本発明の水溶性高分子顔料分散剤に親水性と分散性を付与することができる。親水性と分散性のバランスを良くする点から、炭素数４又は炭素数５のアルキル基を有するα、β−ジカルボン酸が好ましい。より好ましくは、マレイン酸又はイタコン酸である。特に好ましくはイタコン酸である。 The α, β-unsaturated dicarboxylic acid (C) (hereinafter referred to as “component (C)”) is not particularly limited as long as it has an unsaturated bond and two carboxyl groups. Specific examples include maleic acid having 4 carbon atoms, maleic anhydride, fumaric acid, itaconic acid having 5 carbon atoms, citraconic acid, mesaconic acid, chorismic acid having 10 carbon atoms, and the like. Moreover, you may neutralize the carboxyl group of (C) component partially or entirely with a base. Specific examples of the base include sodium hydroxide, potassium hydroxide, ammonia and the like. The component (C) can impart hydrophilicity and dispersibility to the water-soluble polymer pigment dispersant of the present invention. From the viewpoint of improving the balance between hydrophilicity and dispersibility, α, β-dicarboxylic acids having an alkyl group having 4 or 5 carbon atoms are preferred. More preferred is maleic acid or itaconic acid. Particularly preferred is itaconic acid.
上記単量体（Ｄ）（以下、（Ｄ）成分という）は、下記一般式（１）で表わされるものであれば特に限定されず、ビニルスルホン酸、スチレンスルホン酸、２−メチル−２−プロペン−１−スルホン酸（メタリルスルホン酸）、２−アクリルアミド−２−メチルプロパンスルホン酸等の有機スルホン酸系ビニルモノマー類のナトリウム塩、カリウム塩等のアルカリ金属塩、アルカリ土類金属塩等が挙げられる。これらの中で、水への分散性の点においてアルカリ金属塩（一般式（１）におけるＭがアルカリ金属）が好ましい。（Ｄ）成分は、これらの１種又は２種以上を用いることができる。これらの中でも好ましくは、スチレンスルホン酸のアルカリ金属塩、又は、メタリルスルホン酸のアルカリ金属塩であり、より好ましくはスチレンスルホン酸ナトリウム、又はスチレンスルホン酸ナトリウムとメタリルスルホン酸ナトリウムの併用である。（Ｄ）成分により、本発明の水溶性高分子顔料分散剤に親水性を付与することができ、水溶性高分子顔料分散剤と顔料を含む色素を含有する水系組成物の状態を安定させることができる。 The monomer (D) (hereinafter referred to as the component (D)) is not particularly limited as long as it is represented by the following general formula (1), and vinyl sulfonic acid, styrene sulfonic acid, 2-methyl-2- Sodium salts and potassium salts of organic sulfonic acid vinyl monomers such as propene-1-sulfonic acid (methallylsulfonic acid) and 2-acrylamido-2-methylpropanesulfonic acid, alkaline earth metal salts, etc. Is mentioned. Among these, alkali metal salts (M in the general formula (1) is an alkali metal) are preferable from the viewpoint of dispersibility in water. As the component (D), one or more of these may be used. Among these, preferably, an alkali metal salt of styrene sulfonic acid or an alkali metal salt of methallyl sulfonic acid, more preferably sodium styrene sulfonate, or a combination of sodium styrene sulfonate and sodium methallyl sulfonate. . The component (D) can impart hydrophilicity to the water-soluble polymer pigment dispersant of the present invention, and stabilize the state of the water-based composition containing the water-soluble polymer pigment dispersant and a pigment containing a pigment. Can do.
本発明の水溶性高分子顔料分散剤は、上記（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分を必須構成成分とする共重合体を含むものである。なお、これらの成分以外に必要に応じて、スチレンなどを含むことができる。これにより、芳香環を持つような顔料に対する分散剤の吸着力を向上させることが可能となる。 The water-soluble polymer pigment dispersant of the present invention contains a copolymer having the above component (A), component (B), component (C) and component (D) as essential components. In addition to these components, styrene or the like can be included as necessary. Thereby, it becomes possible to improve the adsorptive power of the dispersant to the pigment having an aromatic ring.
上記共重合体に用いる各成分の割合は、顔料への分散剤の吸着性及び水への分散性の点から、（Ａ）成分が３０〜７５重量％、（Ｂ）成分が１５〜４０重量％、（Ｃ）成分が５〜３０重量％、（Ｄ）成分が５〜１５重量％であることが好ましい。より好ましくは、（Ａ）成分が３５〜６２．５重量％、（Ｂ）成分が２０〜３５重量％、（Ｃ）成分が１０〜２５重量％、（Ｄ）成分の割合が７．５〜１２．５重量％である。スチレン等の（Ａ）〜（Ｄ）成分以外のその他の使用量としては、（Ａ）〜（Ｄ）成分の合計を１００重量％としたときに０〜２０重量％であることが好ましい。 The proportion of each component used in the copolymer is 30 to 75% by weight for the component (A) and 15 to 40% by weight for the component (B) from the viewpoint of the adsorptivity of the dispersant to the pigment and the dispersibility in water. %, The component (C) is preferably 5 to 30% by weight, and the component (D) is preferably 5 to 15% by weight. More preferably, the component (A) is 35 to 62.5% by weight, the component (B) is 20 to 35% by weight, the component (C) is 10 to 25% by weight, and the proportion of the component (D) is 7.5 to 7.5%. 12.5% by weight. The amount of use other than the components (A) to (D) such as styrene is preferably 0 to 20% by weight when the total of the components (A) to (D) is 100% by weight.
本発明の水溶性高分子顔料分散剤の製造方法は、特に限定されず、溶液重合、乳化重合、懸濁重合等の各種公知の方法を用いることができる。 The production method of the water-soluble polymer pigment dispersant of the present invention is not particularly limited, and various known methods such as solution polymerization, emulsion polymerization and suspension polymerization can be used.
上記溶液重合による場合には、イソプロピルアルコール、エチルアルコール、メチルイソブチルケトン等の溶媒を使用できる。 In the case of the above solution polymerization, a solvent such as isopropyl alcohol, ethyl alcohol, methyl isobutyl ketone and the like can be used.
上記乳化重合方法で使用する乳化剤としては、特に制限はされず、各種の界面活性剤を使用できる。例えばアニオン性界面活性剤としては、ジアルキルスルホコハク酸塩、アルカンスルホン酸塩、α−オレフィンスルホン酸塩、ポリオキシエチレンアルキルエーテルスルホコハク酸エステル塩、ポリオキシエチレンスチリルフェニルエーテルスルホコハク酸エステル塩、ナフタリンスルホン酸ホルマリン縮合物、ポリオキシエチレンアルキルエーテル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩等を例示でき、ノニオン性界面活性剤としてはポリオキシエチレンアルキルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル及びこれら界面活性剤にビニル基またはアリル基、プロペニル基を導入した反応性界面活性剤等が挙げられる。これら界面活性剤は１種または２種以上を適宜選択して使用することができ、その使用量は全仕込単量体に対して通常は０．１〜１０重量％程度が好ましい。 The emulsifier used in the emulsion polymerization method is not particularly limited, and various surfactants can be used. For example, anionic surfactants include dialkyl sulfosuccinate, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate, polyoxyethylene styryl phenyl ether sulfosuccinate, naphthalene sulfonate Formalin condensate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, etc. can be exemplified, and nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene Examples include sorbitan fatty acid esters and reactive surfactants obtained by introducing a vinyl group, an allyl group, or a propenyl group into these surfactants. These surfactants can be used by appropriately selecting one kind or two or more kinds, and the use amount thereof is usually preferably about 0.1 to 10% by weight with respect to all charged monomers.
上記懸濁重合方法で使用する分散剤としては、特に制限されず、各種の分散剤を使用できる。例えばポリビニルアルコール、ポリビニルアルコール部分ケン化物、リン酸カルシウム等が挙げられる。これら分散剤は１種または２種以上を適宜選択して使用することができ、その使用量は全仕込単体量に対して通常は０．０５〜１重量％程度が好ましい。 The dispersant used in the suspension polymerization method is not particularly limited, and various dispersants can be used. Examples thereof include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate. One or more of these dispersants can be appropriately selected and used, and the amount used is usually preferably about 0.05 to 1% by weight with respect to the total amount of the charged substances.
上記共重合で使用する重合開始剤としては特に限定はされず、過硫酸塩類、過酸化物、アゾ化合物、レドックス系開始剤などの各種のものを使用でき、分子量を調節するために公知の連鎖移動剤であるイソプロピルアルコール、四塩化炭素、エチルベンゼン、イソプロピルベンゼン、クメン、チオグリコール酸エステル、アルキルメルカプタン、２−メルカプトエタノール、２，４−ジフェニル−４−メチル−１−ペンテン等を適宜使用することもできる。 The polymerization initiator used in the copolymerization is not particularly limited, and various types such as persulfates, peroxides, azo compounds, redox initiators can be used, and a known chain is used to adjust the molecular weight. Use isopropyl alcohol, carbon tetrachloride, ethylbenzene, isopropylbenzene, cumene, thioglycolic acid ester, alkyl mercaptan, 2-mercaptoethanol, 2,4-diphenyl-4-methyl-1-pentene, etc. as transfer agents. You can also.
上記共重合体の重量平均分子量は、顔料の分散性、分散安定性と直接相関するため、通常は重量平均分子量が７５００〜２００００、好ましくは１００００〜１３０００である。７５００以上で分散安定性が向上し、２００００以下の場合には顔料への吸着性を向上させることができるとともに、粘度を低下させることができ、ハンドリング性を向上させることができる。なお、重量平均分子量はゲルパーメーションクロマトグラフィーによるポリエチレンオキシド換算値である。 Since the weight average molecular weight of the copolymer directly correlates with the dispersibility and dispersion stability of the pigment, the weight average molecular weight is usually 7500 to 20000, preferably 10,000 to 13000. When it is 7500 or more, the dispersion stability is improved, and when it is 20000 or less, the adsorptivity to the pigment can be improved, the viscosity can be lowered, and the handling property can be improved. In addition, a weight average molecular weight is a polyethylene oxide conversion value by gel permeation chromatography.
上記共重合体の２５重量％溶液における粘度は、ＪＩＳ Ｋ ７１１７−２に準拠し、Ｂ型粘度計を用いて２５℃において測定したとき、ハンドリング性の点から１００〜２０００ｍＰａ・ｓであることが好ましい。より好ましくは、１００〜５００ｍＰａ・ｓである。この範囲の粘度とすることで、優れた顔料の分散性、分散安定性を有するだけでなく、分散安定剤へ顔料を分散する際のハンドリング性を向上させることができ、工業的に有用のものとすることができる。 The viscosity of the copolymer in a 25% by weight solution is 100 to 2000 mPa · s from the viewpoint of handling properties when measured at 25 ° C. using a B-type viscometer in accordance with JIS K 7117-2. preferable. More preferably, it is 100-500 mPa * s. By setting the viscosity within this range, not only has excellent dispersibility and dispersion stability of the pigment, but also the handling properties when dispersing the pigment in the dispersion stabilizer can be improved and industrially useful. It can be.
上記共重合体の２５％溶液における色調は、１ガードナー以下であることが好ましい。これにより、本発明の水溶性高分子顔料分散剤は、色調が低く、インキ・塗料に使用した場合に色味の変化がないため、白色顔料などの明度が高い塗料に好適に利用することができる。 The color tone in a 25% solution of the copolymer is preferably 1 Gardner or less. As a result, the water-soluble polymer pigment dispersant of the present invention has a low color tone and does not change in color when used in inks and paints, so it can be suitably used for paints with high brightness such as white pigments. it can.
水系溶媒中に、本発明の水溶性高分子顔料分散剤と色素を含有し、分散させた水系組成物もまた、本発明の一つである。 An aqueous composition in which the water-soluble polymer pigment dispersant and dye of the present invention are contained and dispersed in an aqueous solvent is also one aspect of the present invention.
上記水系溶媒とは、例えば水、アルコール／水混合液が挙げられる。環境問題や安全性の観点から水が好ましい。これにより、低ＶＯＣ塗料やゼロＶＯＣ塗料として使用可能となる。 Examples of the aqueous solvent include water and alcohol / water mixtures. Water is preferable from the viewpoint of environmental problems and safety. Thereby, it can be used as a low VOC paint or a zero VOC paint.
本発明の水系組成物に含まれる色素としては、有機または無機の顔料、染料を単独でまたは２種類以上混合して用いることができる。 As a pigment | dye contained in the aqueous composition of this invention, an organic or inorganic pigment and dye can be used individually or in mixture of 2 or more types.
上記有機顔料としては、従来公知の種々有機顔料を用いることができる。具体的には、例えば、赤色系有機顔料としては、 Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １、２、３、４、５、６、７、９、１０、１４、１７、２２、２３、３１、３８、４１、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５２：１、５２：２、５３：１、５７：１、６０：１、６３：１、６６、６７、８１：１、８１：２、８１：３、８３、８８、９０、１０５、１１２、１１９、１２２、１２３、１４４、１４６、１４９、１５０、１５５、１６６、１６８、１６９、１７０、１７１、１７２、１７５、１７６、１７７、１７８、１７９、１８４、１８５、１８７、１８８、１９０、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１６、２２０、２２４、２２６、２４２、２４６、２５４、２５５、２６４、２７０、２７２、２７９が挙げられる。 As the organic pigment, various conventionally known organic pigments can be used. Specifically, for example, red organic pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279.
黄色系有機顔料としては、 Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １、２、３、４、５、６、１０、１１、１２、１３、１４、１５、１６、１７、１８、２０、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４２、４３、５３、５５、６０、６１、６２、６３、６５、７３、７４、７７、８１、８３、８６、９３、９４、９５、９７、９８、１００、１０１、１０４、１０６、１０８、１０９、１１０、１１３、１１４、１１５、１１６、１１７、１１８、１１９、１２０、１２３、１２５、１２６、１２７、１２８、１２９、１３７、１３８、１３９、１４７、１４８、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１６１、１６２、１６４、１６６、１６７、１６８、１６９、１７０、１７１、１７２、１７３、１７４、１７５、１７６、１７７、１７９、１８０、１８１、１８２、１８５、１８７、１８８、１９３、１９４、１９９、２１３、２１４が挙げられる。 Examples of yellow organic pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 74,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214 and the like.
橙色系有機顔料としては、Ｃ．Ｉ． Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ ２、５、１３、１６、１７：１、３１、３４、３６、３８、４３、４６、４８、４９、５１、５２、５５、５９、６０、６１、６２、６４、７１、７３が挙げられる。 Examples of orange organic pigments include C.I. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 Can be mentioned.
緑色系有機顔料としては、Ｃ．Ｉ． Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７、１０、３６、３７が挙げられ、青色系有機顔料としては、 Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １、２、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、２２、６０、６４、６６、７９、７９のＣｌ置換基をＯＨに変更したもの、８０が挙げられる。 Examples of green organic pigments include C.I. I. Pigment Green 7, 10, 36, 37, and blue organic pigments include C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH 80.
紫色系有機顔料としては、 Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １、１９、２３、２７、３２、３７、４２が挙げられ、茶色系有機顔料としては、 Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｒｏｗｎ ２５、２８が挙げられ、黒色系有機顔料としては、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌａｃｋ １、７等を挙げることができる。 Examples of purple organic pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and brown organic pigments include C.I. I. Pigment Brown 25 and 28, and black organic pigments include C.I. I. Pigment Black 1, 7 and the like.
上記無機顔料としては、硫酸バリウム、亜鉛華、硫酸鉛、黄色鉛、亜鉛黄、べんがら（赤色酸化鉄（ＩＩＩ））、カドミウム赤、群青、紺青、酸化クロム緑、コバルト緑、アンバー、チタンブラック、合成鉄黒、酸化チタン、四酸化鉄などの金属酸化物粉や、金属硫化物粉や、金属粉等が挙げられる。無機顔料は、彩度と明度のバランスを取りつつ良好な印刷性、粘度安定性等を確保するために、有機顔料と組み合わせて用いることができる。 Examples of the inorganic pigment include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber, titanium black, Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments can be used in combination with organic pigments in order to ensure good printability, viscosity stability and the like while maintaining a balance between chroma and lightness.
本発明の水系組成物において、色調を合わせるためなどの目的で、上記顔料とともに染料を使用することもできる。使用可能な染料としては、特に制限はなく、例えば、特開平７−２８６１０７号公報、特開２００２−１４２２０号公報、特開平８−１７９１２０号公報等に記載の色素である。 In the aqueous composition of the present invention, a dye can be used together with the pigment for the purpose of adjusting the color tone. The dye that can be used is not particularly limited, and examples thereof include the dyes described in JP-A-7-286107, JP-A-2002-14220, JP-A-8-179120, and the like.
上記染料を化学構造別に分類すると、ピラゾールアゾ系、アニリノアゾ系、トリフェニルメタン系、アントラキノン系、アンスラピリドン系、ベンジリデン系、オキソノール系、ピラゾロトリアゾールアゾ系、ピリドンアゾ系、シアニン系、フェノチアジン系、ピロロピラゾールアゾメチン系、キサンテン系、フタロシアニン系、ペンゾピラン系、インジゴ系等の染料が挙げられる。 The above dyes are classified according to chemical structure. Examples include pyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo dyes.
本発明の水系組成物における色素の割合は、組成物全体を１００重量％とした場合に、５０〜８０重量％であることが好ましい。これにより、塗料やインキにした際に、溶媒の比率が高くなり乾燥時間を短くすることができる。 It is preferable that the ratio of the pigment | dye in the aqueous composition of this invention is 50 to 80 weight% when the whole composition is 100 weight%. Thereby, when it is set as a coating material or ink, the ratio of a solvent becomes high and drying time can be shortened.
以下に本発明を実施例により更に具体的に説明する。ただし、本発明はこれら実施例に限定されるものではない。また実施例中、「％」及び「部」は特に断りのない限り「重量％」、「重量部」を意味する。なお、得られた水溶性高分子顔料分散剤の分析は次の方法によって実施した。結果を表１に示す。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. In the examples, “%” and “part” mean “% by weight” and “part by weight” unless otherwise specified. The obtained water-soluble polymer pigment dispersant was analyzed by the following method. The results are shown in Table 1.
（重量平均分子量）
重量平均分子量は、得られた水溶性高分子顔料分散剤をゲルパーミエーションクロマトグラフィー（東ソー（株）製、商品名「ＨＬＣ−８３２０」、カラム：東ソー（株）製、商品名「ＴＳＫ−ＧＥＬ ＧＭＰＷＸＬ」および「ＴＳＫ−ＧＥＬ Ｇ２５００ＰＷＸＬ」を連結）により測定し、ポリエチレンオキシド換算によりを求めた。
(Weight average molecular weight)
The weight average molecular weight is obtained by subjecting the obtained water-soluble polymer pigment dispersant to gel permeation chromatography (manufactured by Tosoh Corporation, trade name “HLC-8320”, column: Tosoh Corporation, trade name “TSK-GEL”). GMPW XL "and" TSK-GEL G2500PW XL "were measured by connection), and determined in terms of polyethylene oxide.
（粘度）
ＪＩＳ Ｋ ７１１７−２に準拠し、Ｂ型粘度計を用いて２５℃において測定した。
(viscosity)
Based on JIS K 7117-2, it measured at 25 degreeC using the B-type viscosity meter.
（色調）
ＪＩＳ Ｋ ００７１−２に準拠しガードナー単位で測定した。
(Color tone)
Based on JIS K 0071-2, measurement was performed in units of Gardner.
製造例−１［水溶性高分子顔料分散剤１の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、アクリルアミド１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が３００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１）を得た。
Production Example-1 [Synthesis of water-soluble polymer pigment dispersant 1]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of acrylamide (45% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl acrylate (22 % By weight), cyclohexyl methacrylate 22 parts (10% by weight), itaconic acid 24 parts (11% by weight), sodium styrenesulfonate 13.5 parts (6% by weight), sodium methallylsulfonate 13.5 parts (6% by weight) % By weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide that neutralizes 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. 300 mPa · s, color tone 1 Gardner An aqueous solution of this copolymer (water-soluble polymer pigment dispersant 1) was obtained.
製造例−２［水溶性高分子顔料分散剤２の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１０重量％）、メタクリル酸シクロヘキシル２７部（１２重量％）、イタコン酸５６部（２５重量％）、スチレンスルホン酸ナトリウム１８部（８重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１００００（ＧＰＣによる。以下同じ）、２５℃における粘度が５００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２）を得た。
Production Example 2 [Synthesis of water-soluble polymer pigment dispersant 2]
In the same reactor as in Production Example 1, 100 parts of acrylamide (45% by weight of the total weight of monomers, the same applies hereinafter), 22 parts (10% by weight) of 2-ethylhexyl acrylate, 27 parts of cyclohexyl methacrylate (12 parts) Weight%), itaconic acid 56 parts (25% by weight), sodium styrenesulfonate 18 parts (8% by weight), ammonium persulfate 5 parts and isopropyl alcohol 14 parts, water 667 parts, mixed and heated at 80 ° C. for 5 hours. Reaction was performed to obtain an aqueous solution of the copolymer. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture was cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 2) having a concentration of 25% weight average molecular weight of 10,000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 500 mPa · s, and a color tone of 1 Gardner. It was.
製造例−３［水溶性高分子顔料分散剤３の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０．８重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２４．９重量％）、イタコン酸２４部（１２．２重量％）、スチレンスルホン酸ナトリウム１２部（６．１重量％）、メタリルスルホン酸ナトリウム１２部（６．１重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１００００（ＧＰＣによる。以下同じ）、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤３）を得た。
Production Example 3 [Synthesis of Water-Soluble Polymer Pigment Dispersant 3]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50.8% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl acrylate (24.9% by weight), 24 itaconic acid Parts (12.2% by weight), sodium styrenesulfonate 12 parts (6.1% by weight), sodium methallylsulfonate 12 parts (6.1% by weight), ammonium persulfate 5 parts and isopropyl alcohol 14 parts, water 667 The parts were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 3) having a concentration of 25% weight average molecular weight of 10,000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 450 mPa · s, and a color tone of 1 Gardner. It was.
製造例−４［水溶性高分子顔料分散剤４の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５１．８重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２５．４重量％）、イタコン酸２４部（１２．４重量％）、スチレンスルホン酸ナトリウム２０部（１０．４重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１００００（ＧＰＣによる。以下同じ）、２５℃における粘度が４００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤４）を得た。
Production Example 4 [Synthesis of Water-Soluble Polymer Pigment Dispersant 4]
In the same reactor as in Production Example 1, 100 parts of acrylamide (51.8% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl acrylate (25.4% by weight), 24 itaconic acid Parts (12.4% by weight), sodium styrenesulfonate 20 parts (10.4% by weight), ammonium persulfate 5 parts and isopropyl alcohol 14 parts, water 667 parts are mixed and heated, and reacted at 80 ° C. for 5 hours. An aqueous solution of the copolymer was obtained. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture was cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 4) having a concentration of 25% weight average molecular weight of 10,000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 400 mPa · s, and a color tone of 1 Gardner. It was.
製造例−５［水溶性高分子顔料分散剤５の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１重量％）、メタクリル酸シクロヘキシル２７部（１３．５重量％）、マレイン酸２４部（１２重量％）、スチレンスルホン酸ナトリウム１３．５部（６．８重量％）、メタリルスルホン酸ナトリウム１３．５部（６．８重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１００００（ＧＰＣによる。以下同じ）、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤５）を得た。
Production Example-5 [Synthesis of Water-soluble Polymer Pigment Dispersant 5]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50% by weight of the total weight of monomers, the same applies hereinafter), 22 parts (11% by weight) of 2-ethylhexyl acrylate, 27 parts of cyclohexyl methacrylate (13 parts) 0.5 wt%), maleic acid 24 parts (12 wt%), sodium styrenesulfonate 13.5 parts (6.8 wt%), sodium methallylsulfonate 13.5 parts (6.8 wt%) 5 parts of ammonium sulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 5) having a concentration of 25% weight average molecular weight of 10,000 (by GPC, the same applies hereinafter), a viscosity at 25 ° C. of 450 mPa · s, and a color tone of 1 Gardner. It was.
製造例−６［水溶性高分子顔料分散剤６の合成］
製造例１と同様の反応装置に、メタクリルアミド１００部（単量体の総重量和の５０．８重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１．２重量％）、メタクリル酸シクロヘキシル２７部（１３．７重量％）、イタコン酸２４部（１２．２重量％）、スチレンスルホン酸ナトリウム１２部（６．１重量％）、メタリルスルホン酸ナトリウム１２部（６．１重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１００００（ＧＰＣによる。以下同じ）、２５℃における粘度が５００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤６）を得た。
Production Example-6 [Synthesis of Water-Soluble Polymer Pigment Dispersant 6]
In the same reactor as in Production Example 1, 100 parts of methacrylamide (50.8% by weight of the total weight of monomers, the same applies hereinafter), 22 parts of 2-ethylhexyl acrylate (11.2% by weight), methacrylic acid Cyclohexyl 27 parts (13.7% by weight), itaconic acid 24 parts (12.2% by weight), sodium styrenesulfonate 12 parts (6.1% by weight), sodium methallylsulfonate 12 parts (6.1% by weight) ), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain an aqueous solution of a copolymer. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 6) having a concentration of 25% weight average molecular weight of 10,000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 500 mPa · s, and a color tone of 1 Gardner. It was.
製造例−７［水溶性高分子顔料分散剤７の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０．８重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１．２重量％）、メタクリル酸シクロヘキシル２７部（１３．７重量％）、イタコン酸２４部（１２．２重量％）、スチレンスルホン酸ナトリウム１２部（６．１重量％）、メタリルスルホン酸ナトリウム１２部（６．１重量％）、過硫酸アンモニウム７．５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量７５００（ＧＰＣによる。以下同じ）、２５℃における粘度が１００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤７）を得た。
Production Example-7 [Synthesis of water-soluble polymer pigment dispersant 7]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50.8% by weight of the total weight of monomers, the same applies hereinafter), 22 parts of 2-ethylhexyl acrylate (11.2% by weight), cyclohexyl methacrylate 27 parts (13.7% by weight), itaconic acid 24 parts (12.2% by weight), sodium styrenesulfonate 12 parts (6.1% by weight), sodium methallylsulfonate 12 parts (6.1% by weight) Then, 7.5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain an aqueous solution of a copolymer. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 7) having a concentration of 25% weight average molecular weight of 7500 (by GPC, the same applies hereinafter), a viscosity at 25 ° C. of 100 mPa · s, and a color tone of 1 Gardner. It was.
製造例−８［水溶性高分子顔料分散剤８の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１重量％）、メタクリル酸シクロヘキシル２７部（１３．５重量％）、イタコン酸２４部（１２重量％）、スチレンスルホン酸ナトリウム２７部（１３．５重量％）、過硫酸アンモニウム２．５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１７５００（ＧＰＣによる。以下同じ）、２５℃における粘度が２０００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤８）を得た。
Production Example-8 [Synthesis of Water-Soluble Polymer Pigment Dispersant 8]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50% by weight of the total weight of monomers, the same applies hereinafter), 22 parts (11% by weight) of 2-ethylhexyl acrylate, 27 parts of cyclohexyl methacrylate (13 parts) 0.5 wt%), 24 parts of itaconic acid (12 wt%), 27 parts of sodium styrenesulfonate (13.5 wt%), 2.5 parts of ammonium persulfate and 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated. The mixture was reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture was cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 8) having a concentration of 25% weight average molecular weight of 17500 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 2000 mPa · s, and a color tone of 1 Gardner. It was.
製造例−９［水溶性高分子顔料分散剤９の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１重量％）、メタクリル酸シクロヘキシル２７部（１３．５重量％）、イタコン酸２４部（１２重量％）、スチレンスルホン酸ナトリウム１３．５部（６．８重量％）、メタリルスルホン酸ナトリウム１３．５部（６．８重量％）、過硫酸アンモニウム２部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量２００００（ＧＰＣによる。以下同じ）、２５℃における粘度が１７５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤９）を得た。
Production Example-9 [Synthesis of Water-Soluble Polymer Pigment Dispersant 9]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50% by weight of the total weight of monomers, the same applies hereinafter), 22 parts (11% by weight) of 2-ethylhexyl acrylate, 27 parts of cyclohexyl methacrylate (13 parts) 0.5 wt%), itaconic acid 24 parts (12 wt%), sodium styrenesulfonate 13.5 parts (6.8 wt%), sodium methallylsulfonate 13.5 parts (6.8 wt%), excess 2 parts of ammonium sulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain an aqueous solution of a copolymer. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 9) having a concentration of 25% weight average molecular weight of 20000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 1750 mPa · s, and a color tone of 1 Gardner. It was.
製造例−１０［水溶性高分子顔料分散剤１０の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１重量％）、メタクリル酸シクロヘキシル２７部（１３．５重量％）、イタコン酸２４部（１２重量％）、スチレンスルホン酸ナトリウム２７部（１３．５重量％）、過硫酸アンモニウム７．５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量７５００（ＧＰＣによる。以下同じ）、２５℃における粘度が２５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１０）を得た。
Production Example-10 [Synthesis of Water-Soluble Polymer Pigment Dispersant 10]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50% by weight of the total weight of monomers, the same applies hereinafter), 22 parts (11% by weight) of 2-ethylhexyl acrylate, 27 parts of cyclohexyl methacrylate (13 parts) 0.5 wt%), 24 parts of itaconic acid (12 wt%), 27 parts of sodium styrenesulfonate (13.5 wt%), 7.5 parts of ammonium persulfate and 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated. The mixture was reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture was cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 10) having a concentration of 25% weight average molecular weight of 7500 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 250 mPa · s, and a color tone of 1 Gardner. It was.
製造例−１１［水溶性高分子顔料分散剤１１の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１重量％）、メタクリル酸シクロヘキシル２７部（１３．５重量％）、イタコン酸２４部（１２重量％）、スチレンスルホン酸ナトリウム１３．５部（６．８重量％）、メタリルスルホン酸ナトリウム１３．５部（６．８重量％）、過硫酸アンモニウム１５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１０００（ＧＰＣによる。以下同じ）、２５℃における粘度が５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１１）を得た。
Production Example 11 [Synthesis of water-soluble polymer pigment dispersant 11]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50% by weight of the total weight of monomers, the same applies hereinafter), 22 parts (11% by weight) of 2-ethylhexyl acrylate, 27 parts of cyclohexyl methacrylate (13 parts) 0.5 wt%), itaconic acid 24 parts (12 wt%), sodium styrenesulfonate 13.5 parts (6.8 wt%), sodium methallylsulfonate 13.5 parts (6.8 wt%), excess 15 parts of ammonium sulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain an aqueous solution of a copolymer. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 11) having a concentration of 25% weight average molecular weight of 1000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 50 mPa · s, and a color tone of 1 Gardner. It was.
製造例−１２［水溶性高分子顔料分散剤１２の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０重量％、以下同様）、アクリル酸２−エチルヘキシル２２部（１１重量％）、メタクリル酸シクロヘキシル２７部（１３．５重量％）、イタコン酸２４部（１２重量％）、スチレンスルホン酸ナトリウム２７部（１３．５重量％）、過硫酸アンモニウム０．５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１０００００（ＧＰＣによる。以下同じ）、２５℃における粘度が１００００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１２）を得た。
Production Example-12 [Synthesis of Water-soluble Polymer Pigment Dispersant 12]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50% by weight of the total weight of monomers, the same applies hereinafter), 22 parts (11% by weight) of 2-ethylhexyl acrylate, 27 parts of cyclohexyl methacrylate (13 parts) 0.5 wt%), 24 parts of itaconic acid (12 wt%), 27 parts of sodium styrenesulfonate (13.5 wt%), 0.5 parts of ammonium persulfate and 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated. The mixture was reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, an aqueous solution (water-soluble polymer pigment dispersant 12) of a copolymer having a concentration of 25% weight average molecular weight of 100,000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 10,000 mPa · s, and a color tone of 1 Gardner is obtained. It was.
製造例−１３［水溶性高分子顔料分散剤１３の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、Ｎ，Ｎ−ジメチルアミノメタクリル酸メチル１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１３）を得た。
Production Example 13 [Synthesis of Water-Soluble Polymer Pigment Dispersant 13]
In a reaction vessel equipped with a stirrer, thermometer, reflux condenser, and nitrogen introduction tube, 100 parts of methyl N, N-dimethylaminomethacrylate (45% by weight of the total weight of monomers, the same applies hereinafter), acrylic 2-ethylhexyl acid 49 parts (22% by weight), cyclohexyl methacrylate 22 parts (10% by weight), itaconic acid 24 parts (11% by weight), sodium styrenesulfonate 13.5 parts (6% by weight), methallylsulfone 13.5 parts (6% by weight) of sodium acid, 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. 450 mPa · s, color tone 1 Gardner An aqueous solution of the copolymer (water-soluble polymer pigment dispersant 13) was obtained.
製造例−１４［水溶性高分子顔料分散剤１４の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、Ｎ−（２−メタクリロイルオキシエチル）エチレン尿素１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が４００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１４）を得た。
Production Example-14 [Synthesis of Water-soluble Polymer Pigment Dispersant 14]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of N- (2-methacryloyloxyethyl) ethylene urea (45% by weight of the total weight of monomers, the same applies hereinafter) , 49 parts (22% by weight) of 2-ethylhexyl acrylate, 22 parts (10% by weight) of cyclohexyl methacrylate, 24 parts (11% by weight) of itaconic acid, 13.5 parts (6% by weight) of sodium styrenesulfonate, 13.5 parts (6% by weight) of sodium rylsulfonate, 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. 400 mPa · s, color tone 1 Gardner An aqueous solution of the copolymer (water-soluble polymer pigment dispersant 14) was obtained.
製造例−１５［水溶性高分子顔料分散剤１５の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、Ｎ−ビニル−２ピロリドン１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１５）を得た。
Production Example-15 [Synthesis of Water-soluble Polymer Pigment Dispersant 15]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of N-vinyl-2pyrrolidone (45% by weight of the total weight of monomers, the same applies hereinafter), acrylic acid 2- 49 parts (22% by weight) ethylhexyl, 22 parts (10% by weight) cyclohexyl methacrylate, 24 parts (11% by weight) itaconic acid, 13.5 parts (6% by weight) sodium styrenesulfonate, 13 sodium methallylsulfonate 5 parts (6% by weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain an aqueous solution of a copolymer. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. 450 mPa · s, color tone 1 Gardner An aqueous solution of the copolymer (water-soluble polymer pigment dispersant 15) was obtained.
製造例−１６［水溶性高分子顔料分散剤１６の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、Ｎ−ビニルモルホリン１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１６）を得た。
Production Example-16 [Synthesis of water-soluble polymer pigment dispersant 16]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of N-vinylmorpholine (45% by weight of the total weight of monomers, the same applies hereinafter), 2-ethylhexyl acrylate 49 Parts (22% by weight), cyclohexyl methacrylate 22 parts (10% by weight), itaconic acid 24 parts (11% by weight), sodium styrenesulfonate 13.5 parts (6% by weight), sodium methallylsulfonate 13.5 Parts (6% by weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. 450 mPa · s, color tone 1 Gardner An aqueous solution of the copolymer (water-soluble polymer pigment dispersant 16) was obtained.
製造例−１７［水溶性高分子顔料分散剤１７の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、２−ビニルピリジン１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が４００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１７）を得た。
Production Example-17 [Synthesis of Water-soluble Polymer Pigment Dispersant 17]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of 2-vinylpyridine (45% by weight of the total weight of monomers, the same applies hereinafter), 2-ethylhexyl acrylate 49 Parts (22% by weight), cyclohexyl methacrylate 22 parts (10% by weight), itaconic acid 24 parts (11% by weight), sodium styrenesulfonate 13.5 parts (6% by weight), sodium methallylsulfonate 13.5 Parts (6% by weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. 400 mPa · s, color tone 1 Gardner An aqueous solution of this copolymer (water-soluble polymer pigment dispersant 17) was obtained.
製造例−１８［水溶性高分子顔料分散剤１８の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、ジメチルアミノメチルスチレン１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１８）を得た。
Production Example-18 [Synthesis of Water-Soluble Polymer Pigment Dispersant 18]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of dimethylaminomethylstyrene (45% by weight of the total weight of monomers, the same applies hereinafter), 2-ethylhexyl acrylate 49 Parts (22% by weight), cyclohexyl methacrylate 22 parts (10% by weight), itaconic acid 24 parts (11% by weight), sodium styrenesulfonate 13.5 parts (6% by weight), sodium methallylsulfonate 13.5 Parts (6% by weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. 450 mPa · s, color tone 1 Gardner An aqueous solution of this copolymer (water-soluble polymer pigment dispersant 18) was obtained.
製造例−１９［水溶性高分子顔料分散剤１９の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の５０重量％、以下同様）、メタクリル酸２−エチルヘキシル４９部（２４．５重量％）、イタコン酸２４部（１２重量％）、スチレンスルホン酸ナトリウム２７部（１３．５重量％）、過硫酸アンモニウム４．５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１２０００（ＧＰＣによる。以下同じ）、２５℃における粘度が５５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤１９）を得た。
Production Example-19 [Synthesis of water-soluble polymer pigment dispersant 19]
In the same reactor as in Production Example 1, 100 parts of acrylamide (50% by weight of the total weight of monomers, the same applies hereinafter), 49 parts (24.5% by weight) of 2-ethylhexyl methacrylate, 24 parts of itaconic acid ( 12% by weight), 27 parts (13.5% by weight) of sodium styrenesulfonate, 4.5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and the reaction was carried out at 80 ° C. for 5 hours. A combined aqueous solution was obtained. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture is cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 19) having a concentration of 25% weight average molecular weight of 12000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 550 mPa · s, and a color tone of 1 Gardner. It was.
製造例−２０［水溶性高分子顔料分散剤２０の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の４５重量％、以下同様）、メタクリル酸２−エチルヘキシル４９部（２２重量％）、アクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム２７部（１２重量％）、過硫酸アンモニウム７．５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量７５００（ＧＰＣによる。以下同じ）、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２０）を得た。
Production Example-20 [Synthesis of Water-Soluble Polymer Pigment Dispersant 20]
In the same reactor as in Production Example 1, 100 parts of acrylamide (45% by weight of the total weight of monomers, the same applies hereinafter), 49 parts (22% by weight) of 2-ethylhexyl methacrylate, 22 parts of cyclohexyl acrylate (10% % By weight), 24 parts (11% by weight) itaconic acid, 27 parts (12% by weight) sodium styrenesulfonate, 7.5 parts ammonium persulfate and 14 parts isopropyl alcohol, and 667 parts water, and heated at 80 ° C. Reaction was performed for 5 hours to obtain an aqueous solution of the copolymer. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture was cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 20) having a concentration of 25% weight average molecular weight of 7500 (by GPC, the same applies hereinafter), a viscosity at 25 ° C. of 450 mPa · s, and a color tone of 1 Gardner. It was.
製造例−２１［水溶性高分子顔料分散剤２１の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の４８．８重量％、以下同様）、メタクリル酸２−エチルヘキシル４９部（２３．９重量％）、アクリル酸シクロヘキシル２２部（１０．７重量％）、イタコン酸２４部（１１．７重量％）、スチレンスルホン酸ナトリウム２７部（４．９重量％）、過硫酸アンモニウム７．５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１０００（ＧＰＣによる。以下同じ）、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２１）を得た。
Production Example 21 [Synthesis of water-soluble polymer pigment dispersant 21]
In the same reaction apparatus as in Production Example 1, 100 parts of acrylamide (48.8% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl methacrylate (23.9% by weight), cyclohexyl acrylate 22 parts (10.7% by weight), itaconic acid 24 parts (11.7% by weight), sodium styrenesulfonate 27 parts (4.9% by weight), ammonium persulfate 7.5 parts and isopropyl alcohol 14 parts, water 667 The parts were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 21) having a concentration of 25% weight average molecular weight of 1000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 450 mPa · s, and a color tone of 1 Gardner. It was.
製造例−２２［水溶性高分子顔料分散剤２２の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、アクリルアミド１００部（単量体の総重量和の４５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２２重量％）、メタクリル酸シクロヘキシル２２部（１０重量％）、イタコン酸２４部（１１重量％）、スチレンスルホン酸ナトリウム１３．５部（６重量％）、メタリルスルホン酸ナトリウム１３．５部（６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和するアンモニアを加えて１時間攪拌して、濃度２５％、重量平均分子量１００００、２５℃における粘度が４５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２２）を得た。
Production Example-22 [Synthesis of Water-soluble Polymer Pigment Dispersant 22]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of acrylamide (45% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl acrylate (22 % By weight), cyclohexyl methacrylate 22 parts (10% by weight), itaconic acid 24 parts (11% by weight), sodium styrenesulfonate 13.5 parts (6% by weight), sodium methallylsulfonate 13.5 parts (6% by weight) % By weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, ammonia that neutralizes 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 10,000, viscosity at 25 ° C. was 450 mPa · s, and color tone was 1 Gardner. An aqueous polymer solution (water-soluble polymer pigment dispersant 22) was obtained.
製造例−２３［水溶性高分子顔料分散剤２３の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の６６．２重量％、以下同様）、イタコン酸２４部（１５．９重量％）、スチレンスルホン酸ナトリウム１３．５部（８．９重量％）、メタリルスルホン酸ナトリウム１３．５部（８．９重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１５０００（ＧＰＣによる。以下同じ）、２５℃における粘度が７５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２３）を得た。
Production Example-23 [Synthesis of Water-soluble Polymer Pigment Dispersant 23]
In the same reactor as in Production Example 1, 100 parts of acrylamide (66.2% by weight of the total weight of monomers, the same applies hereinafter), 24 parts of itaconic acid (15.9% by weight), sodium styrenesulfonate 13. 5 parts (8.9% by weight), 13.5 parts (8.9% by weight) of sodium methallylsulfonate, 5 parts of ammonium persulfate and 14 parts of isopropyl alcohol, and 667 parts of water were mixed and heated. A time reaction was performed to obtain an aqueous solution of the copolymer. Further, 33 parts of water was added and IPA was distilled off. Thereafter, cooling is performed to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 23) having a concentration of 25% weight average molecular weight of 15000 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 750 mPa · s, and a color tone of 1 Gardner. It was.
製造例−２４［水溶性高分子顔料分散剤２４の合成］
製造例１と同様の反応装置に、アクリルアミド１００部（単量体の総重量和の６６．２重量％、以下同様）、イタコン酸２４部（１５．９重量％）、スチレンスルホン酸ナトリウム２７部（１７．８重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％重量平均分子量１４５００（ＧＰＣによる。以下同じ）、２５℃における粘度が７００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２４）を得た。
Production Example-24 [Synthesis of Water-soluble Polymer Pigment Dispersant 24]
In the same reactor as in Production Example 1, 100 parts of acrylamide (66.2% by weight of the total weight of monomers, the same applies hereinafter), 24 parts of itaconic acid (15.9% by weight), 27 parts of sodium styrenesulfonate (17.8% by weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture is cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 24) having a concentration of 25% weight average molecular weight of 14500 (according to GPC, the same applies hereinafter), a viscosity at 25 ° C. of 700 mPa · s, and a color tone of 1 Gardner. It was.
製造例−２５［水溶性高分子顔料分散剤２５の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、アクリルアミド１００部（単量体の総重量和の５０．５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２４．７重量％）、メタクリル酸シクロヘキシル２２部（１１．１重量％）、スチレンスルホン酸ナトリウム１３．５部（６．８重量％）、メタリルスルホン酸ナトリウム１３．５部（６．８重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％、重量平均分子量１７５００、２５℃における粘度が８００ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２５）を得た。
Production Example-25 [Synthesis of Water-Soluble Polymer Pigment Dispersant 25]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of acrylamide (50.5% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl acrylate (24.7% by weight), cyclohexyl methacrylate 22 parts (11.1% by weight), sodium styrenesulfonate 13.5 parts (6.8% by weight), sodium methallylsulfonate 13.5 parts (6.8%) % By weight), 5 parts of ammonium persulfate, 14 parts of isopropyl alcohol and 667 parts of water were mixed and heated, and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture was cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 25) having a concentration of 25%, a weight average molecular weight of 17500, a viscosity at 25 ° C. of 800 mPa · s, and a color tone of 1 Gardner.
製造例−２６［水溶性高分子顔料分散剤２６の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、アクリルアミド１００部（単量体の総重量和の５０．５重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２４．７重量％）、メタクリル酸シクロヘキシル２２部（１１．１重量％）、スチレンスルホン酸ナトリウム２７部（１３．６重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、濃度２５％、重量平均分子量１８０００、２５℃における粘度が８５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２６）を得た。
Production Example-26 [Synthesis of Water-soluble Polymer Pigment Dispersant 26]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of acrylamide (50.5% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl acrylate (24.7% by weight), cyclohexyl methacrylate 22 parts (11.1% by weight), sodium styrenesulfonate 27 parts (13.6% by weight), ammonium persulfate 5 parts and isopropyl alcohol 14 parts, water 667 parts -Heated and reacted at 80 ° C for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. Thereafter, the mixture was cooled to obtain a copolymer aqueous solution (water-soluble polymer pigment dispersant 26) having a concentration of 25%, a weight average molecular weight of 18000, a viscosity at 25 ° C. of 850 mPa · s, and a color tone of 1 Gardner.
製造例−２７［水溶性高分子顔料分散剤２７の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、アクリルアミド１００部（単量体の総重量和の５１．３重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２５．１重量％）、メタクリル酸シクロヘキシル２２部（１１．３重量％）、イタコン酸２４部（１２．３重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量６０００、２５℃における粘度が５０ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２７）を得た。
Production Example 27 [Synthesis of water-soluble polymer pigment dispersant 27]
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of acrylamide (51.3% by weight of the total weight of monomers, the same applies hereinafter), 49 parts of 2-ethylhexyl acrylate (25.1 wt%), cyclohexyl methacrylate 22 parts (11.3 wt%), itaconic acid 24 parts (12.3 wt%), ammonium persulfate 5 parts and isopropyl alcohol 14 parts, water 667 parts mixed and heated The reaction was carried out at 80 ° C. for 5 hours to obtain an aqueous solution of the copolymer. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 6000, viscosity at 25 ° C. 50 mPa · s, color tone 1 Gardner An aqueous solution of this copolymer (water-soluble polymer pigment dispersant 27) was obtained.
製造例−２８［水溶性高分子顔料分散剤２８の合成］
撹拌装置、温度計、還流冷却管、および窒素導入管を備えた反応容器に、メタクリルアミド１００部（単量体の総重量和の５１．３重量％、以下同様）、アクリル酸２−エチルヘキシル４９部（２５．１重量％）、メタクリル酸シクロヘキシル２２部（１１．３重量％）、イタコン酸２４部（１２．３重量％）、過硫酸アンモニウム５部及びイソプロピルアルコール１４部、水６６７部を混合・加熱し、８０℃で５時間反応を行い共重合体の水溶液を得た。さらに水３３部を加え、ＩＰＡを留去した。その後冷却し、６０℃でイタコン酸の５０％を中和する水酸化ナトリウムを加えて１時間攪拌して、濃度２５％、重量平均分子量７０００、２５℃における粘度が７５ｍＰａ・ｓ、色調が１ガードナーの共重合体の水溶液（水溶性高分子顔料分散剤２８）を得た。
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 100 parts of methacrylamide (51.3% by weight of the total weight of monomers, the same applies hereinafter), 2-ethylhexyl acrylate 49 Parts (25.1% by weight), cyclohexyl methacrylate 22 parts (11.3% by weight), itaconic acid 24 parts (12.3% by weight), ammonium persulfate 5 parts and isopropyl alcohol 14 parts, water 667 parts. The mixture was heated and reacted at 80 ° C. for 5 hours to obtain a copolymer aqueous solution. Further, 33 parts of water was added and IPA was distilled off. After cooling, sodium hydroxide neutralizing 50% of itaconic acid at 60 ° C. was added and stirred for 1 hour. Concentration 25%, weight average molecular weight 7000, viscosity at 25 ° C. 75 mPa · s, color tone 1 Gardner An aqueous solution of this copolymer (water-soluble polymer pigment dispersant 28) was obtained.
実施例１［水系組成物１の調製］
製造例１で得た水溶性高分子顔料分散剤１を２部及びチタン白顔料（石原産業（株）製ＣＲ−９０）１００部に水９４部及びガラスビーズ１００部を加え ペイントシェーカーにて１時間、分散を行った。分散工程の後、金網を使用してガラスビーズを除き、分散剤の添加量が０．５％（対顔料 固形分換算（％））の水系組成物１を得た。水溶性高分子顔料分散剤１を４部及びチタン白顔料（石原産業（株）製ＣＲ−９０）１００部に水９４部及びガラスビーズ１００部を加えペイントシェーカーにて１時間、分散を行った。分散工程の後、金網を使用してガラスビーズを除き、分散剤の添加量が１．０％（対顔料 固形分換算（％））の水系組成物１を得た。水溶性高分子顔料分散剤１を８部及びチタン白顔料（石原産業製ＣＲ−９０）１００部に水９４部及びガラスビーズ１００部を加えペイントシェーカーにて１時間、分散を行った。分散工程の後、金網を使用してガラスビーズを除き、分散剤の添加量が２．０％（対顔料 固形分換算（％））の水系組成物１を得た。得られた水系組成物１の２５℃における粘度を測定した。また、得られた水系組成物１を径１６ｍｍ、高さ１５０ｍｍの試験管に入れ、１日後、７日後の経時での分離度を測定した。分離度は（離水層の高さ（ｍｍ））÷（全液量の高さ（ｍｍ））×１００（％）にて求めた。分離度が低いほど、良好な貯蔵安定性を有する。結果を表２に示す。
Example 1 [Preparation of aqueous composition 1]
2 parts of the water-soluble polymer pigment dispersant 1 obtained in Production Example 1 and 100 parts of titanium white pigment (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) were added with 94 parts of water and 100 parts of glass beads. Time and dispersion were performed. After the dispersion step, the glass beads were removed using a wire mesh to obtain an aqueous composition 1 having a dispersant addition amount of 0.5% (vs. pigment solid content conversion (%)). 4 parts of water-soluble polymer pigment dispersant 1 and 100 parts of titanium white pigment (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) were added with 94 parts of water and 100 parts of glass beads and dispersed for 1 hour in a paint shaker. . After the dispersion step, the glass beads were removed using a wire mesh, and an aqueous composition 1 having a dispersant addition amount of 1.0% (vs. pigment solid content conversion (%)) was obtained. 8 parts of the water-soluble polymer pigment dispersant 1 and 100 parts of titanium white pigment (CR-90 manufactured by Ishihara Sangyo Co., Ltd.) were added with 94 parts of water and 100 parts of glass beads, and dispersed in a paint shaker for 1 hour. After the dispersion step, the glass beads were removed using a wire mesh, and an aqueous composition 1 having a dispersant addition amount of 2.0% (vs. pigment solid content conversion (%)) was obtained. The viscosity of the obtained aqueous composition 1 at 25 ° C. was measured. The obtained aqueous composition 1 was put in a test tube having a diameter of 16 mm and a height of 150 mm, and the degree of separation over time was measured after 1 day and after 7 days. The degree of separation was determined by (height of water separation layer (mm)) / (height of total liquid amount (mm)) × 100 (%). The lower the degree of separation, the better the storage stability. The results are shown in Table 2.
実施例２〜２２［水系組成物２〜２２の調製］
実施例１における水溶性高分子顔料分散剤を製造例２〜２２で得た水溶性高分子顔料分散剤２〜２２に変更した以外は同様に分散を行い、分散剤の添加量が０．５％、１．０％、２．０％（対顔料 固形分換算）となる３種類の水系組成物２〜２２を得た。この水系組成物２〜２２の粘度、分離度を実施例１と同様に測定した。結果を表２に示す。
Examples 2 to 22 [Preparation of aqueous compositions 2 to 22]
Dispersion was performed in the same manner except that the water-soluble polymer pigment dispersant in Example 1 was changed to the water-soluble polymer pigment dispersants 2 to 22 obtained in Production Examples 2 to 22, and the added amount of the dispersant was 0.5. Three types of aqueous compositions 2 to 22 having%, 1.0%, and 2.0% (in terms of pigment solid content) were obtained. The viscosity and the degree of separation of these aqueous compositions 2 to 22 were measured in the same manner as in Example 1. The results are shown in Table 2.
比較例１［水系組成物２３の調製］
実施例１における水溶性高分子顔料分散剤をディスコートＮ−１４（第一工業製薬製特殊ポリカルボン酸塩）に変更した以外は同様に分散を行い、分散剤の添加量が０．５％、１．０％、２．０％（対顔料 固形分換算）となる３種類の水系組成物２３を得た。この水系組成物２３の粘度、分離度を実施例１と同様に測定した。結果を表２に示す。
Comparative Example 1 [Preparation of aqueous composition 23]
Dispersion was performed in the same manner except that the water-soluble polymer pigment dispersant in Example 1 was changed to DISCOAT N-14 (Daiichi Kogyo Seiyaku special polycarboxylate), and the amount of dispersant added was 0.5%. Thus, three types of aqueous compositions 23 having 1.0% and 2.0% (in terms of pigment solid content) were obtained. The viscosity and the degree of separation of this aqueous composition 23 were measured in the same manner as in Example 1. The results are shown in Table 2.
比較例２〜７［水系組成物２４〜２９の調製］
実施例１における水溶性高分子顔料分散剤を製造例２３〜２８で得た水溶性高分子顔料分散剤２３〜２８に変更した以外は同様に分散を行い、分散剤の添加量が０．５％、１．０％、２．０％（対顔料 固形分換算）となる３種類の水系組成物２４〜２９を得た。この水系組成物２４〜２９の粘度、分離度を実施例１と同様に測定した。結果を表２に示す。
Comparative Examples 2 to 7 [Preparation of aqueous compositions 24-29]
Dispersion was carried out in the same manner except that the water-soluble polymer pigment dispersant in Example 1 was changed to the water-soluble polymer pigment dispersants 23 to 28 obtained in Production Examples 23 to 28, and the amount of dispersant added was 0.5. Three types of aqueous compositions 24 to 29 having%, 1.0%, and 2.0% (based on pigment solid content) were obtained. The viscosity and the degree of separation of these aqueous compositions 24 to 29 were measured in the same manner as in Example 1. The results are shown in Table 2.
Claims (8)
An aqueous composition containing the water-soluble polymer pigment dispersant according to any one of claims 1 to 7 and a dye in an aqueous solvent.
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| JP2019019293A (en) * | 2017-07-21 | 2019-02-07 | 花王株式会社 | Pigment water dispersion, and aqueous ink |
| JPWO2018168486A1 (en) * | 2017-03-14 | 2019-03-22 | Dic株式会社 | Aqueous pigment dispersion and method for producing aqueous pigment dispersion |
| JP2019081890A (en) * | 2017-10-30 | 2019-05-30 | 荒川化学工業株式会社 | Aqueous precoated metal coating resin |
| CN115785324A (en) * | 2023-02-09 | 2023-03-14 | 广东壮丽彩印股份有限公司 | Preparation method of dispersing agent for nano calcium carbonate |
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| JPWO2018168486A1 (en) * | 2017-03-14 | 2019-03-22 | Dic株式会社 | Aqueous pigment dispersion and method for producing aqueous pigment dispersion |
| JP2019019293A (en) * | 2017-07-21 | 2019-02-07 | 花王株式会社 | Pigment water dispersion, and aqueous ink |
| JP7031943B2 (en) | 2017-07-21 | 2022-03-08 | 花王株式会社 | Pigment water dispersion and water-based ink |
| JP2019081890A (en) * | 2017-10-30 | 2019-05-30 | 荒川化学工業株式会社 | Aqueous precoated metal coating resin |
| CN115785324A (en) * | 2023-02-09 | 2023-03-14 | 广东壮丽彩印股份有限公司 | Preparation method of dispersing agent for nano calcium carbonate |
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