JP5448650B2 - Method for producing aqueous pigment dispersion - Google Patents
Method for producing aqueous pigment dispersion Download PDFInfo
- Publication number
- JP5448650B2 JP5448650B2 JP2009200712A JP2009200712A JP5448650B2 JP 5448650 B2 JP5448650 B2 JP 5448650B2 JP 2009200712 A JP2009200712 A JP 2009200712A JP 2009200712 A JP2009200712 A JP 2009200712A JP 5448650 B2 JP5448650 B2 JP 5448650B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- pigment
- dispersion
- aqueous
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000049 pigment Substances 0.000 title claims description 169
- 239000006185 dispersion Substances 0.000 title claims description 141
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000012528 membrane Substances 0.000 claims description 97
- 238000011282 treatment Methods 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 229920003176 water-insoluble polymer Polymers 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 46
- 239000007787 solid Substances 0.000 claims description 29
- -1 alkali metal salt Chemical class 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 22
- 239000003431 cross linking reagent Substances 0.000 claims description 21
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 17
- 239000012466 permeate Substances 0.000 claims description 16
- 239000008151 electrolyte solution Substances 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 238000009295 crossflow filtration Methods 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 42
- 239000002245 particle Substances 0.000 description 40
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 33
- 239000000178 monomer Substances 0.000 description 29
- 238000003860 storage Methods 0.000 description 27
- 238000001914 filtration Methods 0.000 description 20
- 229920006037 cross link polymer Polymers 0.000 description 17
- 238000004132 cross linking Methods 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- 235000002639 sodium chloride Nutrition 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000001965 increasing effect Effects 0.000 description 9
- 230000003472 neutralizing effect Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 7
- 238000000108 ultra-filtration Methods 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 229920002492 poly(sulfone) Polymers 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000001471 micro-filtration Methods 0.000 description 3
- 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 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- XPZQBGDNVOHQIS-UHFFFAOYSA-N 2,9-dichloro-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=C(Cl)C=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1)Cl)N1)C1=C2 XPZQBGDNVOHQIS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 description 2
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- 229910000619 316 stainless steel Inorganic materials 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 2
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- DGBWPZSGHAXYGK-UHFFFAOYSA-N perinone Chemical compound C12=NC3=CC=CC=C3N2C(=O)C2=CC=C3C4=C2C1=CC=C4C(=O)N1C2=CC=CC=C2N=C13 DGBWPZSGHAXYGK-UHFFFAOYSA-N 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical compound S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- JMEWGCRUPXQFQL-UHFFFAOYSA-N 1,2-dichloro-5,12-dihydroquinolino[2,3-b]acridine-7,14-dione Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C(C(=O)C=1C(=CC=C(C=1Cl)Cl)N1)C1=C2 JMEWGCRUPXQFQL-UHFFFAOYSA-N 0.000 description 1
- 229940015975 1,2-hexanediol Drugs 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ATKFMEGWDYLXBP-UHFFFAOYSA-N 2-(2,4,5-trichlorophenoxy)ethanol Chemical compound OCCOC1=CC(Cl)=C(Cl)C=C1Cl ATKFMEGWDYLXBP-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
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- KKKKCPPTESQGQH-UHFFFAOYSA-N 2-(4,5-dihydro-1,3-oxazol-2-yl)-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=NCCO1 KKKKCPPTESQGQH-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- HMOZDINWBHMBSQ-UHFFFAOYSA-N 2-[3-(4,5-dihydro-1,3-oxazol-2-yl)phenyl]-4,5-dihydro-1,3-oxazole Chemical compound O1CCN=C1C1=CC=CC(C=2OCCN=2)=C1 HMOZDINWBHMBSQ-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 239000010963 304 stainless steel Substances 0.000 description 1
- BFEJTCHFLJECJN-UHFFFAOYSA-N 4,11-Dichloro-5,12-dihydroquino[2,3-b]acridine-7,14-dione Chemical compound N1C2=C(Cl)C=CC=C2C(=O)C2=C1C=C(C(C=1C=CC=C(C=1N1)Cl)=O)C1=C2 BFEJTCHFLJECJN-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000001744 Sodium fumarate Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 235000003591 Tagetes lucida Nutrition 0.000 description 1
- 240000002670 Tagetes lucida Species 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- CHIHQLCVLOXUJW-UHFFFAOYSA-N benzoic anhydride Chemical compound C=1C=CC=CC=1C(=O)OC(=O)C1=CC=CC=C1 CHIHQLCVLOXUJW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000010866 blackwater Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- BCFSVSISUGYRMF-UHFFFAOYSA-N calcium;dioxido(dioxo)chromium;dihydrate Chemical compound O.O.[Ca+2].[O-][Cr]([O-])(=O)=O BCFSVSISUGYRMF-UHFFFAOYSA-N 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011026 diafiltration Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VPWFPZBFBFHIIL-UHFFFAOYSA-L disodium 4-[(4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 VPWFPZBFBFHIIL-UHFFFAOYSA-L 0.000 description 1
- MSJMDZAOKORVFC-SEPHDYHBSA-L disodium fumarate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C\C([O-])=O MSJMDZAOKORVFC-SEPHDYHBSA-L 0.000 description 1
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 210000001699 lower leg Anatomy 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000001042 pigment based ink Substances 0.000 description 1
- 210000003339 pole cell Anatomy 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940005573 sodium fumarate Drugs 0.000 description 1
- 235000019294 sodium fumarate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000626 sulfinic acid group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 235000013706 tagetes lucida Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Description
本発明は、水系顔料分散体の製造方法、その方法により得られるインクジェット記録用水系顔料分散体、及びそれを含有するインクジェット記録用水系インクに関する。 The present invention relates to a method for producing an aqueous pigment dispersion, an aqueous pigment dispersion for ink jet recording obtained by the method, and an aqueous ink for ink jet recording containing the same.
インクジェット記録方式は、非常に微細なノズルからインク液滴を記録部材に直接吐出し、付着させて文字や画像を得る記録方式である。この方式は、フルカラー化が容易でかつ安価であり、記録部材として普通紙が使用可能で、被印刷物に対して非接触、という多くの利点があるため普及が著しい。中でも印字物の耐光性や耐水性の観点から顔料系インクが主流となってきている。
近年、インクジェット記録ヘッドの高精細化により、ノズル径が小さくなり、更には印刷の高速化に伴い、吐出性や保存安定性の更なる向上が求められている。
The ink jet recording method is a recording method in which characters and images are obtained by ejecting ink droplets directly from a very fine nozzle onto a recording member and attaching them. This method is easily spread at full color and inexpensive, and can be used for recording paper as a recording member, and has many advantages in that it is non-contact with the substrate, so that it is widely used. Among these, pigment-based inks have become mainstream from the viewpoint of light resistance and water resistance of printed matter.
In recent years, with the increase in definition of an ink jet recording head, the nozzle diameter has become smaller, and further, with the increase in printing speed, further improvements in ejection properties and storage stability have been demanded.
特許文献１には、顔料を皮膜形成性樹脂で被覆した着色マイクロカプセルを水性媒体中に含むインクであって、皮膜形成性樹脂のうちインク中に溶解する樹脂成分が０．０１〜２質量％である着色マイクロカプセル分散型水性ジェットインクが開示されている。
しかしながら、特許文献１のインクにおいては、皮膜形成樹脂成分が、水溶性ポリマーや自己分散ポリマーとしてインク中に溶解するため、保存安定性や吐出性が満足できるものではない。
特許文献２には、親水性の分散性付与基を顔料粒子表面に導入する工程Ａと、工程Ａで得られた顔料を水系媒体中に分散する工程Ｂと、工程Ｂで得られた分散液に限外ろ過処理及び／又は沈降ろ過処理を施す工程Ｃとからなる顔料分散液の製造方法が開示されている。
この特許文献２の実施例によれば、顔料分散液について限外濾過を行い、限外濾過の繰り返しによる環流液の顔料濃度の上昇は、イオン交換水を添加することで調節している。そして濾過液の電気伝導率が１Ｓ／ｍの時点で顔料濃度が１０〜２０％の最終環流液を取り出している。
しかしながら、特許文献２の方法は精製効率や生産性において満足できるものではない。
Patent Document 1 discloses an ink containing colored microcapsules in which a pigment is coated with a film-forming resin in an aqueous medium, and 0.01 to 2% by mass of a resin component dissolved in the ink among the film-forming resin. A colored microcapsule-dispersed water-based jet ink is disclosed.
However, in the ink of Patent Document 1, since the film-forming resin component is dissolved in the ink as a water-soluble polymer or a self-dispersing polymer, the storage stability and the ejectability are not satisfactory.
Patent Document 2 discloses a process A for introducing a hydrophilic dispersibility-imparting group onto the surface of pigment particles, a process B for dispersing the pigment obtained in process A in an aqueous medium, and a dispersion obtained in process B. Discloses a process for producing a pigment dispersion comprising the step C of performing ultrafiltration treatment and / or sedimentation filtration treatment.
According to the example of Patent Document 2, ultrafiltration is performed on the pigment dispersion, and the increase in the pigment concentration of the reflux liquid due to repeated ultrafiltration is adjusted by adding ion-exchanged water. Then, when the electrical conductivity of the filtrate is 1 S / m, the final reflux liquid having a pigment concentration of 10 to 20% is taken out.
However, the method of Patent Document 2 is not satisfactory in terms of purification efficiency and productivity.
水系顔料分散体や水系インクの吐出性や保存安定性を改善するために、それらを膜処理することは公知である。水系顔料分散体等の膜処理において、生産性を高めるためには、それらを高濃度な状態で処理することが有効であるが、水系顔料分散体等の粘度が高くなると繰り返し膜処理を行うことが実質的に困難となり、結果的にインクの保存安定性、ひいては吐出性が十分に改善されなかった。
本発明は、膜処理法により、生産性よく保存安定性の優れた水系顔料分散体を製造する方法、その方法により得られるインクジェット記録用水系顔料分散体、及びそれを含有するインクジェット記録用水系インクを提供することを課題とする。
In order to improve the dischargeability and storage stability of water-based pigment dispersions and water-based inks, it is known to film-treat them. In order to increase productivity in film treatment of water-based pigment dispersions and the like, it is effective to treat them in a high concentration state, but when the viscosity of water-based pigment dispersions and the like increases, film treatment is repeatedly performed. As a result, the storage stability of the ink, and thus the ejection performance, was not sufficiently improved.
The present invention relates to a method for producing an aqueous pigment dispersion excellent in productivity and storage stability by a film treatment method, an aqueous pigment dispersion for ink jet recording obtained by the method, and an aqueous ink for ink jet recording containing the same. It is an issue to provide.
本発明者は、顔料分散体を特定条件下で膜処理することにより、上記課題を解決しうることを見出した。
すなわち、本発明は、次の〔１〕〜〔３〕を提供する。
〔１〕少なくとも顔料、水不溶性ポリマー、水を含有する混合物を分散処理して得られた、固形分濃度１５重量％以上の水分散体に、電解質を添加し、該水分散体の導電率を〔膜処理前の水分散体の導電率±２５％〕の範囲内に保持しつつ膜処理し、膜処理前における顔料に吸着していない水不溶性ポリマー量の５重量％以上を除去する、水系顔料分散体の製造方法。
〔２〕前記〔１〕の方法により得られるインクジェット記録用水系顔料分散体。
〔３〕前記〔２〕の水系顔料分散体を含有するインクジェット記録用水系インク。
The present inventor has found that the above problem can be solved by subjecting the pigment dispersion to a film treatment under specific conditions.
That is, the present invention provides the following [1] to [3].
[1] An electrolyte is added to an aqueous dispersion having a solid content concentration of 15% by weight or more obtained by dispersing a mixture containing at least a pigment, a water-insoluble polymer and water, and the conductivity of the aqueous dispersion is increased. An aqueous system that removes 5% by weight or more of the amount of the water-insoluble polymer that is not adsorbed to the pigment before the membrane treatment, while keeping the membrane within the range of [conductivity of water dispersion before membrane treatment ± 25%] A method for producing a pigment dispersion.
[2] An aqueous pigment dispersion for inkjet recording obtained by the method of [1].
[3] An aqueous ink for ink-jet recording containing the aqueous pigment dispersion of [2].
本発明によれば、膜処理法により、生産性よく保存安定性の優れた水系顔料分散体を製造する方法、その方法により得られるインクジェット記録用水系顔料分散体、及びそれを含有するインクジェット記録用水系インクを提供することができる。 According to the present invention, a method for producing a water-based pigment dispersion excellent in productivity and storage stability by a film treatment method, a water-based pigment dispersion for ink-jet recording obtained by the method, and water for ink-jet recording containing the same System inks can be provided.
〔インクジェット記録用水系インク〕
本発明の水系顔料分散体の製造方法は、少なくとも顔料、水不溶性ポリマー、水を含有する混合物を分散処理して得られた、固形分濃度１５重量％以上の水分散体に、電解質を添加し、該水分散体の導電率を〔膜処理前の水分散体の導電率±２５％〕の範囲内に保持しつつ膜処理し、膜処理前における顔料に吸着していない水不溶性ポリマー量の５重量％以上を除去することを特徴とする。
以下、本発明に用いられる各成分、製造工程等について説明する。
[Water-based ink for inkjet recording]
The method for producing an aqueous pigment dispersion of the present invention comprises adding an electrolyte to an aqueous dispersion having a solid content concentration of 15% by weight or more obtained by dispersing a mixture containing at least a pigment, a water-insoluble polymer and water. The amount of the water-insoluble polymer not adsorbed by the pigment before the membrane treatment was measured while maintaining the conductivity of the aqueous dispersion within the range of [conductivity of water dispersion before membrane treatment ± 25%]. 5% by weight or more is removed.
Hereinafter, each component used for this invention, a manufacturing process, etc. are demonstrated.
〔顔料〕
本発明に用いられる顔料は、無機顔料及び顔料のいずれであってもよい。また、必要に応じて、それらと体質顔料を併用することもできる。
無機顔料としては、例えば、カーボンブラック、金属酸化物、金属硫化物、金属塩化物等が挙げられる。黒色水系インクにおいては、カーボンブラックが好ましい。カーボンブラックとしては、ファーネスブラック、サーマルランプブラック、アセチレンブラック、チャンネルブラック等が挙げられる。
顔料としては、色相は特に限定されず、赤色、黄色、青色、オレンジ、グリーン等の各種の有彩色顔料を用いることができる。例えば、フタロシアニン顔料、キナクリドン顔料、イソインドリノン顔料、ジオキサジン顔料、ペリレン顔料、ペリノン顔料、チオインジゴ顔料、アントラキノン顔料、キノフタロン顔料、ジアゾ顔料、アゾ顔料等が挙げられる。
例えば、フタロシアニン顔料としては、Ｃ．Ｉ．ピグメント・グリーン７、３６、３７、ピグメント・ブルー１６、７５、１５等、キナクリドン顔料としては、Ｃ．Ｉ．ピグメント・バイオレット１９、４２、Ｃ．Ｉ．ピグメント・レッド１２２、１９２、２０２、２０７、２０９等、ジオキサジン顔料としては、Ｃ．Ｉ．ピグメント・バイオレット２３、３７等、ペリレン顔料としては、Ｃ．Ｉ．ピグメント・レッド１９０、２２４、Ｃ．Ｉ．ピグメント・バイオレット２９等、ペリノン顔料としては、Ｃ．Ｉ．ピグメント・オレンジ４３、Ｃ．Ｉ．ピグメント・レッド１９４等、チオインジゴ顔料としては、Ｃ．Ｉ．ピグメント・レッド８８等、アントラキノン顔料としては、Ｃ．Ｉ．ピグメント・イエロー１４７等、ジアゾ顔料としては、Ｃ．Ｉ．ピグメント・イエロー１３、８３、１８８等、アゾ顔料としては、Ｃ．Ｉ．ピグメント・レッド１８７、１７０、４８、５３、２４７、Ｃ．Ｉ．ピグメント・イエロー７４、１５０、Ｃ．Ｉ．ピグメント・オレンジ６４等が挙げられる。
[Pigment]
The pigment used in the present invention may be either an inorganic pigment or a pigment. If necessary, they can be used in combination with extender pigments.
Examples of the inorganic pigment include carbon black, metal oxide, metal sulfide, and metal chloride. In the black water-based ink, carbon black is preferable. Examples of carbon black include furnace black, thermal lamp black, acetylene black, and channel black.
The hue of the pigment is not particularly limited, and various chromatic pigments such as red, yellow, blue, orange, and green can be used. Examples include phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, diazo pigments, and azo pigments.
For example, phthalocyanine pigments include C.I. I. Pigment Green 7, 36, 37, Pigment Blue 16, 75, 15 and the like, and quinacridone pigments include C.I. I. Pigment violet 19, 42, C.I. I. Pigment Red 122, 192, 202, 207, 209, etc. Examples of the dioxazine pigment include C.I. I. Examples of perylene pigments such as CI Pigment Violet 23 and 37 include C.I. I. Pigment red 190, 224, C.I. I. Examples of perinone pigments such as CI Pigment Violet 29 include C.I. I. Pigment orange 43, C.I. I. Examples of thioindigo pigments such as CI Pigment Red 194 include C.I. I. Examples of anthraquinone pigments such as CI Pigment Red 88 include C.I. I. Examples of diazo pigments such as CI Pigment Yellow 147 include C.I. I. Examples of azo pigments such as CI Pigment Yellow 13, 83, and 188 include C.I. I. Pigment red 187, 170, 48, 53, 247, C.I. I. Pigment yellow 74, 150, C.I. I. And CI Pigment Orange 64.
また、キナクリドン固溶体顔料等の固溶体顔料も好適に用いることができる。キナクリドン固溶体顔料は、β型、γ型等の無置換キナクリドンと、２，９−ジクロルキナクリドン、３，１０−ジクロルキナクリドン、４，１１−ジクロルキナクリドン等のジクロロキナクリドンからなる。キナクリドン系固溶体顔料としては、無置換キナクリドン（Ｃ．Ｉ．ピグメント・バイオレット１９）と２，９−ジクロルキナクリドン（Ｃ．Ｉ．ピグメント・レッド２０２）との組合せからなる固溶体顔料が好ましい。
体質顔料としては、シリカ、炭酸カルシウム、タルク等が挙げられる。
顔料は、分散安定性の観点から、顔料誘導体を含んでいてもよい。顔料誘導体は、スルホン酸基、カルボキシ基、リン酸基、スルフィン酸基、アミノ基、アミド基、イミド基等の極性基を有し、顔料の表面処理剤としての機能を有し、顔料の分散を促進するために用いられる。
Moreover, solid solution pigments, such as a quinacridone solid solution pigment, can also be used suitably. The quinacridone solid solution pigment includes unsubstituted quinacridone such as β-type and γ-type, and dichloroquinacridone such as 2,9-dichloroquinacridone, 3,10-dichloroquinacridone, and 4,11-dichloroquinacridone. As the quinacridone-based solid solution pigment, a solid solution pigment composed of a combination of unsubstituted quinacridone (CI Pigment Violet 19) and 2,9-dichloroquinacridone (CI Pigment Red 202) is preferable.
Examples of extender pigments include silica, calcium carbonate, and talc.
The pigment may contain a pigment derivative from the viewpoint of dispersion stability. The pigment derivative has a polar group such as a sulfonic acid group, a carboxy group, a phosphoric acid group, a sulfinic acid group, an amino group, an amide group, and an imide group, and functions as a pigment surface treatment agent. Used to promote
〔水不溶性ポリマー〕
本発明に用いられる水不溶性ポリマーとは、ポリマー固形分換算１００ｇを１０５℃で２時間乾燥させ、恒量に達した後、２５℃の水１００ｇに溶解させたときに、その溶解量が１０ｇ以下、好ましくは５ｇ以下、更に好ましくは１ｇ以下であるポリマーをいう。該溶解量は、ポリマーが塩生成基を有する場合は、その種類に応じて、ポリマーの塩生成基を酢酸又は水酸化ナトリウムで１００％中和した時の最大溶解量である。
水不溶性ポリマーは、塩生成基含有モノマー（ａ）（以下「（ａ）成分」ということがある）由来の構成単位、疎水性モノマー（ｂ）（以下「（ｂ）成分」ということがある）由来の構成単位及び／又はマクロマー（ｃ）（以下「（ｃ）成分」ということがある）由来の構成単位を含むことが好ましい。
このような水不溶性ポリマーとしては、塩生成基含有モノマー（ａ）、疎水性モノマー（ｂ）、及び／又はマクロマー（ｃ）を含むモノマー混合物（以下「モノマー混合物」ということがある）を共重合してなる水不溶性ビニル系ポリマーが好ましい。
この水不溶性ビニル系ポリマーは、十分な印字濃度を発現させる観点から、（ａ）成分由来の構成単位、又は（ａ）及び（ｂ）成分由来の構成単位を主鎖として有し、（ｃ）成分由来の構成単位を側鎖として有する水不溶性ビニル系グラフトポリマーであることが好ましい。
本発明に用いられるポリマーが、水不溶性グラフトポリマーである場合、［主鎖／側鎖］の重量比は、耐擦過性及び保存安定性を向上させる観点から、１／１〜２０／１であることが好ましく、３／２〜１５／１が更に好ましく、２／１〜１０／１が特に好ましい。なお、重合性官能基は側鎖に含有されるものとして計算する。
(Water-insoluble polymer)
The water-insoluble polymer used in the present invention is obtained by drying 100 g in terms of polymer solid content at 105 ° C. for 2 hours, reaching a constant weight, and then dissolving in 100 g of water at 25 ° C. The polymer is preferably 5 g or less, more preferably 1 g or less. When the polymer has a salt-forming group, the dissolution amount is the maximum dissolution amount when the salt-forming group of the polymer is 100% neutralized with acetic acid or sodium hydroxide, depending on the type.
The water-insoluble polymer is a structural unit derived from a salt-forming group-containing monomer (a) (hereinafter sometimes referred to as “(a) component”), a hydrophobic monomer (b) (hereinafter sometimes referred to as “(b) component”). It is preferable to include a structural unit derived from a structural unit derived from and / or a macromer (c) (hereinafter sometimes referred to as “component (c)”).
As such a water-insoluble polymer, a monomer mixture containing a salt-forming group-containing monomer (a), a hydrophobic monomer (b), and / or a macromer (c) (hereinafter sometimes referred to as “monomer mixture”) is copolymerized. A water-insoluble vinyl polymer is preferred.
This water-insoluble vinyl polymer has, as a main chain, a structural unit derived from the component (a) or a structural unit derived from the components (a) and (b) from the viewpoint of developing a sufficient printing density, and (c) A water-insoluble vinyl-based graft polymer having a constituent unit derived from a component as a side chain is preferred.
When the polymer used in the present invention is a water-insoluble graft polymer, the weight ratio of [main chain / side chain] is 1/1 to 20/1 from the viewpoint of improving scratch resistance and storage stability. It is preferably 3/2 to 15/1, more preferably 2/1 to 10/1. It is calculated that the polymerizable functional group is contained in the side chain.
塩生成基含有モノマー（ａ）は、得られる分散体の保存安定性を高める等の観点から用いられるものであり、カチオン性モノマー、アニオン性モノマー等が挙げられる。カチオン性モノマーとしては、Ｎ，Ｎ-ジメチルアミノエチル（メタ）アクリレート、Ｎ-（Ｎ'，Ｎ'-ジメチルアミノプロピル）（メタ）アクリルアミドが好ましい。
アニオン性モノマーとしては、分散安定性、吐出性等の観点から、不飽和カルボン酸モノマーが好ましく、アクリル酸又はメタクリル酸がより好ましい。上記（ａ）成分は、それぞれ単独で又は２種以上を組み合わせて用いることができる。
疎水性モノマー（ｂ）は、耐水性、耐擦過性、印字濃度の向上等の観点から用いられ、アルキル（メタ）アクリレート、アルキル（メタ）アクリルアミド、芳香環含有モノマー等が挙げられる。
The salt-forming group-containing monomer (a) is used from the viewpoint of enhancing the storage stability of the resulting dispersion, and examples thereof include a cationic monomer and an anionic monomer. As the cationic monomer, N, N-dimethylaminoethyl (meth) acrylate and N- (N ′, N′-dimethylaminopropyl) (meth) acrylamide are preferable.
The anionic monomer is preferably an unsaturated carboxylic acid monomer, more preferably acrylic acid or methacrylic acid, from the viewpoints of dispersion stability, dischargeability, and the like. The said (a) component can be used individually or in combination of 2 or more types, respectively.
The hydrophobic monomer (b) is used from the viewpoint of water resistance, scratch resistance, printing density improvement, and the like, and examples thereof include alkyl (meth) acrylate, alkyl (meth) acrylamide, and aromatic ring-containing monomers.
マクロマー（ｃ）は、顔料やシリカ粒子を水不溶性ポリマーで安定分散させる等の観点から用いられ、数平均分子量が５００〜１００，０００、好ましくは１，０００〜１０，０００で、片末端に不飽和基等の重合性官能基を有するモノマーであるマクロマーが挙げられる。
なお、マクロマー（ｃ）の数平均分子量は、標準物質としてポリスチレンを用い、溶媒として５０ミリモル／Ｌの酢酸を含有するテトラヒドロフランを用いたゲルパーミエーションクロマトグラフィーによって測定することができる。
マクロマー（ｃ）としては、片末端に重合性官能基を有するスチレン系マクロマーが顔料との親和性が高く、保存安定性を向上させる観点から好ましい。
The macromer (c) is used from the viewpoint of stably dispersing pigments and silica particles with a water-insoluble polymer, and has a number average molecular weight of 500 to 100,000, preferably 1,000 to 10,000. Examples include macromers that are monomers having a polymerizable functional group such as a saturated group.
The number average molecular weight of the macromer (c) can be measured by gel permeation chromatography using polystyrene as a standard substance and tetrahydrofuran containing 50 mmol / L acetic acid as a solvent.
As the macromer (c), a styrenic macromer having a polymerizable functional group at one end is preferable from the viewpoint of high affinity with the pigment and improving storage stability.
本発明においては、上記（ａ）、（ｂ）、（ｃ）各成分を含むモノマー混合物は、水分散体の分散安定性を高める観点から、更に水酸基含有モノマー（ｄ）（以下「（ｄ）成分」ということがある）を含有することが好ましい。
（ｄ）成分としては、２-ヒドロキシエチル（メタ）アクリレート、ポリエチレングリコールモノメタクリレート、ポリプロピレングリコールメタクリレートが好ましい。
上記モノマー混合物は、水性インクの吐出安定性を高める観点から、更に下記式（１）で表されるモノマー（ｅ）（以下「（ｅ）成分」ということがある）を含有することができる。
ＣＨ2＝Ｃ（Ｒ1）ＣＯＯ（Ｒ2Ｏ）pＲ3 （１）
（式中、Ｒ1は水素原子又は炭素数１〜５のアルキル基を示し、Ｒ2はヘテロ原子を有していてもよい炭素数１〜３０の２価の炭化水素基を示し、Ｒ3はヘテロ原子を有していてもよい炭素数１〜３０の１価の炭化水素基を示すが、ｐは平均付加モル数を示し、１〜６０、好ましくは１〜３０の数である。）
（ｅ）成分としては、メトキシポリエチレングリコール（ｐ＝１〜３０）（メタ）アクリレートが好ましい。
商業的に入手しうる（ｄ）、（ｅ）成分の具体例としては、新中村化学工業株式会社の多官能性アクリレートモノマー（ＮＫエステル）Ｍ−４０Ｇ,９０Ｇ,２３０Ｇ,日本油脂株式会社のブレンマーシリーズ、ＰＥ−９０,２００,３５０，ＰＭＥ−１００,２００,４００,１０００、ＰＰ−１０００,ＰＰ−５００，ＰＰ−８００,ＡＰ−１５０,ＡＰ−４００,ＡＰ−５５０,ＡＰ−８００,５０ＰＥＰ−３００,５０ＰＯＥＰ−８００Ｂ等が挙げられる。
上記（ａ）〜（ｅ）成分は、それぞれ単独で又は２種以上を組み合わせて用いることができる。
In the present invention, the monomer mixture containing the above components (a), (b), and (c) may further contain a hydroxyl group-containing monomer (d) (hereinafter referred to as “(d)” from the viewpoint of improving the dispersion stability of the aqueous dispersion. It is preferable to contain a "component".
As the component (d), 2-hydroxyethyl (meth) acrylate, polyethylene glycol monomethacrylate, and polypropylene glycol methacrylate are preferable.
The monomer mixture may further contain a monomer (e) represented by the following formula (1) (hereinafter also referred to as “component (e)”) from the viewpoint of improving the ejection stability of the water-based ink.
CH 2 = C (R 1) COO (R 2 O) p R 3 (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 represents a divalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom, R 3 Represents a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a hetero atom, but p represents the average number of added moles, and is 1 to 60, preferably 1 to 30.)
As the component (e), methoxypolyethylene glycol (p = 1 to 30) (meth) acrylate is preferable.
Specific examples of commercially available (d) and (e) components include: Shin-Nakamura Chemical Co., Ltd., polyfunctional acrylate monomer (NK ester) M-40G, 90G, 230G; Mer series, PE-90, 200, 350, PME-100, 200, 400, 1000, PP-1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP -300,50POEP-800B etc. are mentioned.
The above components (a) to (e) can be used alone or in combination of two or more.
水不溶性ポリマー製造時における、上記（ａ）〜（ｅ）成分のモノマー混合物中における含有量（未中和量としての含有量。以下同じ）又は水不溶性ポリマー中における（ａ）〜（ｅ）成分に由来する構成単位の含有量は、得られる分散体の保存安定性、印字濃度等の観点から、次のとおりであることが好ましい。
（ａ）成分の含有量は、好ましくは３〜３０重量％、より好ましくは４〜２０重量％であり、（ｂ）成分の含有量は、好ましくは１０〜７０重量％、より好ましくは１５〜６０重量％であり、（ｃ）成分の含有量は、好ましくは１〜２５重量％、より好ましくは５〜２０重量％である。
（ａ）成分の含有量と、（ｂ）成分と（ｃ）成分の合計含有量との重量比（（ａ）／［（ｂ）＋（ｃ）］）は、好ましくは０．０１〜１、より好ましくは０．０２〜０．６７、更に好ましくは０．０３〜０．５０である。
（ｄ）成分の含有量は、好ましくは５〜４０重量％、より好ましくは７〜３０重量％であり、（ｅ）成分の含有量は、好ましくは５〜５０重量％、より好ましくは１０〜４０重量％である。
（ａ）成分と（ｄ）成分との合計含有量は、好ましくは６〜６０重量％、より好ましくは１０〜５０重量％であり、（ａ）成分と（ｅ）成分の合計含有量は、好ましくは６〜７５重量％、より好ましくは１３〜５０重量％であり、（ａ）成分と（ｄ）成分と（ｅ）成分との合計含有量は、好ましくは６〜６０重量％、より好ましくは７〜５０重量％である。
Components (a) to (e) in the monomer mixture of the above components (a) to (e) at the time of production of the water-insoluble polymer (contents as an unneutralized amount; the same applies hereinafter) or the components (a) to (e) in the water-insoluble polymer The content of the structural unit derived from is preferably as follows from the viewpoints of storage stability, print density and the like of the resulting dispersion.
The content of the component (a) is preferably 3 to 30% by weight, more preferably 4 to 20% by weight, and the content of the component (b) is preferably 10 to 70% by weight, more preferably 15 to The content of component (c) is preferably 1 to 25% by weight, more preferably 5 to 20% by weight.
The weight ratio ((a) / [(b) + (c)]) of the content of the component (a) and the total content of the component (b) and the component (c) is preferably 0.01 to 1. More preferably, it is 0.02-0.67, More preferably, it is 0.03-0.50.
The content of component (d) is preferably 5 to 40% by weight, more preferably 7 to 30% by weight, and the content of component (e) is preferably 5 to 50% by weight, more preferably 10 to 10%. 40% by weight.
The total content of the component (a) and the component (d) is preferably 6 to 60% by weight, more preferably 10 to 50% by weight. The total content of the component (a) and the component (e) is Preferably it is 6 to 75% by weight, more preferably 13 to 50% by weight, and the total content of component (a), component (d) and component (e) is preferably 6 to 60% by weight, more preferably Is 7 to 50% by weight.
〔水不溶性ポリマーの製造〕
前記水不溶性ポリマーは、塊状重合法、溶液重合法、懸濁重合法、乳化重合法等の公知の重合法により、モノマー混合物を共重合させることによって製造される。これらの重合法の中では、溶液重合法が好ましい。
溶液重合法で用いる溶媒としては、特に限定されないが、極性有機溶媒が好ましい。極性有機溶媒が水混和性を有する場合には、水と混合して用いることもできる。極性有機溶媒としては、例えば、メタノール、エタノール、プロパノール等の炭素数１〜３の脂肪族アルコール；アセトン、メチルエチルケトン等のケトン類；酢酸エチル等のエステル類等が挙げられる。これらの中では、メタノール、エタノール、アセトン、メチルエチルケトン又はこれらの１種以上と水との混合溶媒が好ましい。
重合の際には、２，２'−アゾビスイソブチロニトリル、２，２'−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ化合物や、ｔ−ブチルペルオキシオクトエート、ジベンゾイルオキシド等の有機過酸化物等の公知のラジカル重合開始剤を用いることができる。ラジカル重合開始剤の量は、モノマー混合物１モルあたり、好ましくは０．００１〜５モル、より好ましくは０．０１〜２モルである。
重合の際には、さらに、オクチルメルカプタン、２−メルカプトエタノール等のメルカプタン類、チウラムジスルフィド類等の公知の重合連鎖移動剤を添加してもよい。
(Production of water-insoluble polymer)
The water-insoluble polymer is produced by copolymerizing a monomer mixture by a known polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. Among these polymerization methods, the solution polymerization method is preferable.
The solvent used in the solution polymerization method is not particularly limited, but a polar organic solvent is preferable. When the polar organic solvent is miscible with water, it can be used by mixing with water. Examples of the polar organic solvent include aliphatic alcohols having 1 to 3 carbon atoms such as methanol, ethanol and propanol; ketones such as acetone and methyl ethyl ketone; esters such as ethyl acetate and the like. Among these, methanol, ethanol, acetone, methyl ethyl ketone, or a mixed solvent of one or more of these and water is preferable.
In the polymerization, azo compounds such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), t-butyl peroxyoctate, dibenzoyl oxide, etc. Known radical polymerization initiators such as organic peroxides can be used. The amount of the radical polymerization initiator is preferably 0.001 to 5 mol, more preferably 0.01 to 2 mol, per mol of the monomer mixture.
In the polymerization, a known polymerization chain transfer agent such as mercaptans such as octyl mercaptan and 2-mercaptoethanol and thiuram disulfide may be further added.
モノマー混合物の重合条件は、使用するラジカル重合開始剤、モノマー、溶媒の種類等によって異なるので一概には決定することができない。通常、重合温度は、好ましくは３０〜１００℃、より好ましくは５０〜８０℃であり、重合時間は、好ましくは１〜２０時間である。また、重合雰囲気は、窒素ガス雰囲気、アルゴン等の不活性ガス雰囲気であることが好ましい。
重合反応の終了後、反応溶液から再沈澱、溶媒留去等の公知の方法により、生成したポリマーを単離することができる。また、得られたポリマーは、再沈澱を繰り返したり、膜分離、クロマトグラフ法、抽出法等により、未反応のモノマー等を除去して精製することができる。
Since the polymerization conditions of the monomer mixture vary depending on the type of radical polymerization initiator, monomer, and solvent used, it cannot be determined unconditionally. Usually, the polymerization temperature is preferably 30 to 100 ° C, more preferably 50 to 80 ° C, and the polymerization time is preferably 1 to 20 hours. The polymerization atmosphere is preferably a nitrogen gas atmosphere or an inert gas atmosphere such as argon.
After completion of the polymerization reaction, the produced polymer can be isolated from the reaction solution by a known method such as reprecipitation or solvent distillation. Further, the obtained polymer can be purified by repeating reprecipitation or by removing unreacted monomers and the like by membrane separation, chromatographic method, extraction method and the like.
本発明で用いられるポリマーの重量平均分子量は、インクの印字濃度及び分散安定性の観点から、５，０００〜５０万が好ましく、１万〜４０万がより好ましく、１万〜３０万が更に好ましく、２万〜２５万が更に好ましい。なお、ポリマーの重量平均分子量は、実施例で示す方法により測定される。
本発明で用いられるポリマーは、（ａ）塩生成基含有モノマー由来の塩生成基を有している場合は中和剤により中和して用いる。中和剤としては、ポリマー中の塩生成基の種類に応じて、酸又は塩基を使用することができる。例えば、塩酸、酢酸、プロピオン酸、リン酸、硫酸、乳酸、コハク酸、グリコール酸、グルコン酸、グリセリン酸等の酸、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、アンモニア、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、トリエタノールアミン、トリブチルアミン等の塩基が挙げられる。
The weight average molecular weight of the polymer used in the present invention is preferably 5,000 to 500,000, more preferably 10,000 to 400,000, and still more preferably 10,000 to 300,000, from the viewpoint of ink printing density and dispersion stability. 20,000 to 250,000 is more preferable. In addition, the weight average molecular weight of a polymer is measured by the method shown in an Example.
When the polymer used in the present invention has (a) a salt-forming group derived from a salt-forming group-containing monomer, it is neutralized with a neutralizing agent. As the neutralizing agent, an acid or a base can be used depending on the type of the salt-forming group in the polymer. For example, hydrochloric acid, acetic acid, propionic acid, phosphoric acid, sulfuric acid, lactic acid, succinic acid, glycolic acid, gluconic acid, glyceric acid and other acids, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonia, methylamine, dimethylamine , Bases such as trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine.
ポリマーの塩生成基の中和度は、保存安定性の観点から、１０〜２００％であることが好ましく、２０〜１５０％であることがより好ましく、５０〜１５０％であることがより好ましく、６０〜１００％であることが更に好ましい。
ポリマーを架橋させる場合は、架橋前のポリマーの塩生成基の中和度は、保存安定性と架橋効率の観点から、１０〜９０％であることが好ましく、２０〜８０％であることがより好ましく、３０〜８０％であることが更に好ましい。
ここで中和度は、塩生成基がアニオン性基である場合、下記式によって求めることができる。
｛［中和剤の重量（ｇ）／中和剤の当量］／［ポリマーの酸価（ＫＯＨｍｇ／ｇ）×ポリマーの重量（ｇ）／（５６×１０００）］｝×１００
塩生成基がカチオン性基である場合は、下記式によって求めることができる。
｛［中和剤の重量（ｇ）／中和剤の当量］／［ポリマーのアミン価（ＨＣＬｍｇ／ｇ）×ポリマーの重量（ｇ）／（３６．５×１０００）］｝×１００
酸価やアミン価は、ポリマーの構成単位から、計算で算出することができる。又は、適当な溶剤（例えばメチルエチルケトン）にポリマーを溶解して、滴定する方法でも求めることができる。
From the viewpoint of storage stability, the degree of neutralization of the salt-forming groups of the polymer is preferably 10 to 200%, more preferably 20 to 150%, more preferably 50 to 150%, More preferably, it is 60 to 100%.
When the polymer is crosslinked, the degree of neutralization of the salt-forming groups of the polymer before crosslinking is preferably 10 to 90%, more preferably 20 to 80%, from the viewpoint of storage stability and crosslinking efficiency. Preferably, it is 30 to 80%.
Here, the degree of neutralization can be determined by the following formula when the salt-forming group is an anionic group.
{[Weight of neutralizing agent (g) / equivalent of neutralizing agent] / [acid value of polymer (KOH mg / g) × polymer weight (g) / (56 × 1000)]} × 100
When the salt-forming group is a cationic group, it can be determined by the following formula.
{[Weight of neutralizer (g) / equivalent of neutralizer] / [amine value of polymer (HCL mg / g) × polymer weight (g) / (36.5 × 1000)]} × 100
The acid value and amine value can be calculated from the structural unit of the polymer. Alternatively, it can also be determined by a method in which a polymer is dissolved in a suitable solvent (for example, methyl ethyl ketone) and titrated.
［水系顔料分散体の製造］
本発明の水系顔料分散体の製造方法に特に制限はないが、下記の工程（１）〜（２）を有する方法により、顔料を含有する水不溶性ポリマー粒子の水分散体を得た後、好ましくは、更に下記工程（３）を有する方法により、顔料を含有する架橋ポリマー粒子の水分散体を得た後、下記工程（４）を有する方法によれば、本発明の水系顔料分散体を効率的に製造することができる。
工程（１）：水不溶性ポリマー、有機溶媒、顔料、水、及び必要に応じて中和剤を含有する混合物を分散処理して、顔料を含有する水不溶性ポリマー粒子の分散体を得る工程
工程（２）：工程（１）で得られた分散体から前記有機溶媒を除去して、顔料を含有する水不溶性ポリマー粒子の水分散体を得る工程
工程（３）：工程（２）で得られた顔料を含有する水不溶性ポリマー粒子のポリマーを架橋剤で架橋させて、顔料を含有する架橋ポリマー粒子の水分散体を得る工程
工程（４）：工程（２）又は（３）で得られた固形分濃度１５重量％以上の水分散体に、電解質を添加し、該水分散体の導電率を〔膜処理前の水分散体の導電率±２５％〕の範囲内に保持しつつ膜処理し、膜処理前における顔料に吸着していない水不溶性ポリマー量の５重量％以上を除去する工程
[Production of water-based pigment dispersion]
Although there is no restriction | limiting in particular in the manufacturing method of the water-based pigment dispersion of this invention, After obtaining the water dispersion of the water-insoluble polymer particle containing a pigment by the method which has the following process (1)-(2), After obtaining an aqueous dispersion of crosslinked polymer particles containing a pigment by a method further comprising the following step (3), the method comprising the following step (4) is effective for the aqueous pigment dispersion of the present invention. Can be manufactured automatically.
Step (1): A step of dispersing a mixture containing a water-insoluble polymer, an organic solvent, a pigment, water and, if necessary, a neutralizing agent to obtain a dispersion of water-insoluble polymer particles containing the pigment. 2): Step of removing the organic solvent from the dispersion obtained in step (1) to obtain an aqueous dispersion of water-insoluble polymer particles containing pigment Step (3): obtained in step (2) Step of cross-linking the polymer of water-insoluble polymer particles containing pigment with a cross-linking agent to obtain an aqueous dispersion of cross-linked polymer particles containing pigment Step (4): Solid obtained in step (2) or (3) An electrolyte is added to an aqueous dispersion having a concentration of 15% by weight or more, and the membrane is treated while maintaining the conductivity of the aqueous dispersion within the range of [conductivity of water dispersion before membrane treatment ± 25%]. The amount of water-insoluble polymer not adsorbed on the pigment before membrane treatment Removing the least weight%
工程（１）
工程（１）では、まず、水不溶性ポリマーを有機溶媒に溶解させ、次に顔料、水、及び必要に応じて中和剤、界面活性剤等を、得られた有機溶媒溶液に加えて混合し、水中油型の分散体を得る方法が好ましい。水不溶性ポリマーの有機溶媒溶液に加える順序に制限はないが、中和剤、水、顔料の順に加えることが好ましい。
混合物中、顔料は、５〜５０重量％が好ましく、１０〜４０重量％が更に好ましく、有機溶媒は、１０〜７０重量％が好ましく、１０〜５０重量％が更に好ましく、水不溶性ポリマーは、２〜４０重量％が好ましく、３〜２０重量％が更に好ましく、水は、１０〜７０重量％が好ましく、２０〜７０重量％が更に好ましい。
水不溶性ポリマーの量に対する顔料の量の重量比〔顔料／水不溶性ポリマー〕は、分散安定性の観点から、５０／５０〜９０／１０であることが好ましく、７０／３０〜８５／１５であることがより好ましい。
Process (1)
In step (1), first, the water-insoluble polymer is dissolved in an organic solvent, and then a pigment, water, and, if necessary, a neutralizing agent and a surfactant are added to the obtained organic solvent solution and mixed. A method for obtaining an oil-in-water type dispersion is preferred. Although there is no restriction | limiting in the order added to the organic solvent solution of a water-insoluble polymer, It is preferable to add in order of a neutralizer, water, and a pigment.
In the mixture, the pigment is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, the organic solvent is preferably 10 to 70% by weight, more preferably 10 to 50% by weight, and the water-insoluble polymer is 2%. -40% by weight is preferred, 3-20% by weight is more preferred, and water is preferably 10-70% by weight, more preferably 20-70% by weight.
The weight ratio of the amount of pigment to the amount of water-insoluble polymer [pigment / water-insoluble polymer] is preferably 50/50 to 90/10, and preferably 70/30 to 85/15 from the viewpoint of dispersion stability. It is more preferable.
ポリマーが塩生成基を有する場合、中和剤を用いることが好ましい。中和剤を用いて中和する場合の中和度には、特に限定がない。通常、最終的に得られる水分散体の液性が中性、例えば、ｐＨが４．５〜１０であることが好ましい。前記ポリマーの望まれる中和度により、ｐＨを決めることもできる。中和剤としては、前記のものが挙げられる。また、ポリマーを予め中和しておいてもよい。
有機溶媒としては、エタノール、イソプロパノール、イソブタノール等のアルコール系溶媒、アセトン、メチルエチルケトン、メチルイソブチルケトン、ジエチルケトン等のケトン系溶媒及びジブチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系溶媒が挙げられる。好ましくは、水１００ｇに対する溶解量が２０℃において、好ましくは５ｇ以上、更に好ましくは１０ｇ以上であり、より具体的には、好ましくは５〜８０ｇ、更に好ましくは１０〜５０ｇのものであり、特に、メチルエチルケトン及びメチルイソブチルケトンが好ましい。
When the polymer has a salt-forming group, it is preferable to use a neutralizing agent. There is no particular limitation on the degree of neutralization when neutralizing with a neutralizer. Usually, it is preferable that the liquid dispersion of the finally obtained water dispersion is neutral, for example, pH is 4.5 to 10. The pH can also be determined by the desired degree of neutralization of the polymer. Examples of the neutralizing agent include those described above. Further, the polymer may be neutralized in advance.
Examples of the organic solvent include alcohol solvents such as ethanol, isopropanol and isobutanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone, and ether solvents such as dibutyl ether, tetrahydrofuran and dioxane. Preferably, the amount dissolved in 100 g of water at 20 ° C. is preferably 5 g or more, more preferably 10 g or more, more specifically preferably 5 to 80 g, more preferably 10 to 50 g, especially Methyl ethyl ketone and methyl isobutyl ketone are preferred.
工程（１）における混合物の分散方法に特に制限はない。本分散だけで顔料を含有する水不溶性ポリマー粒子の平均粒径を所望の粒径となるまで微粒化することもできるが、好ましくは予備分散させた後、さらに剪断応力を加えて本分散を行い、顔料を含有する水不溶性ポリマー粒子の平均粒径を所望の粒径とするよう制御することが好ましい。工程（１）の分散における温度は、０〜４０℃が好ましく、５〜３０℃がより好ましく、分散時間は１〜３０時間が好ましく、２〜２５時間がより好ましい。
混合物を予備分散させる際には、アンカー翼等の一般に用いられている混合撹拌装置を用いることができる。混合撹拌装置の中では、ウルトラディスパー〔浅田鉄工株式会社、商品名〕、エバラマイルダー〔株式会社荏原製作所、商品名〕、ＴＫホモミクサー〔プライミクス株式会社、商品名〕等の高速攪拌混合装置が好ましい。
本分散の剪断応力を与える手段としては、例えば、ロールミル、ビーズミル、ニーダー、エクストルーダ等の混練機、高圧ホモゲナイザー〔株式会社イズミフードマシナリ、商品名〕、ミニラボ8.3H型〔Rannie社、商品名〕に代表されるホモバルブ式の高圧ホモジナイザー、マイクロフルイダイザー〔Microfluidics社、商品名〕、ナノマイザー〔ナノマイザー株式会社、商品名〕等のチャンバー式の高圧ホモジナイザー等が挙げられる。これらの装置は複数を組み合わせることもできる。これらの中では、顔料の小粒子径化の観点から、高圧ホモジナイザーが好ましい。
There is no restriction | limiting in particular in the dispersion method of the mixture in process (1). Although the average particle size of the water-insoluble polymer particles containing the pigment can be atomized only by the main dispersion until the desired particle size is obtained, it is preferably preliminarily dispersed and then subjected to the main dispersion by further applying shear stress. The average particle size of the water-insoluble polymer particles containing the pigment is preferably controlled to a desired particle size. The temperature in the dispersion in the step (1) is preferably 0 to 40 ° C, more preferably 5 to 30 ° C, and the dispersion time is preferably 1 to 30 hours, and more preferably 2 to 25 hours.
When preliminarily dispersing the mixture, a commonly used mixing and stirring device such as an anchor blade can be used. Among the mixing and stirring apparatuses, high-speed stirring and mixing apparatuses such as Ultra Disper [Asada Tekko Co., Ltd., trade name], Ebara Milder [Ebara Manufacturing Co., Ltd., trade name], TK Homomixer [Primix Co., Ltd., trade name] are preferable. .
As means for applying the shear stress of this dispersion, for example, a kneader such as a roll mill, a bead mill, a kneader, an extruder, a high-pressure homogenizer (Izumi Food Machinery Co., Ltd., trade name), a minilab 8.3H type (Rannie Co., trade name) Examples thereof include chamber type high-pressure homogenizers such as homo-valve type high-pressure homogenizers, microfluidizers (trade name), and nanomizers (trade name). A plurality of these devices can be combined. Among these, a high-pressure homogenizer is preferable from the viewpoint of reducing the particle size of the pigment.
工程（２）
工程（２）では、得られた分散体から、公知の方法で有機溶媒を留去することで、顔料を含有する水不溶性ポリマー粒子の水分散体を得ることができる。得られた顔料を含有する水不溶性ポリマー粒子を含む水分散体中の有機溶媒は実質的に除去されていることが好ましいが、本発明の目的を損なわない限り、残存していてもよく、架橋工程を後に行う場合は、必要により架橋後に再除去すればよい。残留有機溶媒の量は０．１重量％以下が好ましく、０．０１重量％以下であることがより好ましい。
また必要に応じて、有機溶媒を留去する前に分散体を加熱撹拌処理することもできる。
得られた顔料を含有する水不溶性ポリマー粒子の水分散体は、顔料を含有する該ポリマーの固体分が水を主媒体とする中に分散しているものである。ここで、ポリマー粒子の形態は特に制限はなく、少なくとも顔料と水不溶性ポリマーにより粒子が形成されていればよい。例えば、該ポリマーに顔料が内包された粒子形態、該ポリマー中に顔料が均一に分散された粒子形態、該ポリマー粒子表面に顔料が露出された粒子形態等が含まれ、これらの混合物も含まれる。
Process (2)
In step (2), an aqueous dispersion of water-insoluble polymer particles containing a pigment can be obtained by distilling off the organic solvent from the obtained dispersion by a known method. The organic solvent in the aqueous dispersion containing the water-insoluble polymer particles containing the obtained pigment is preferably substantially removed, but may remain as long as the object of the present invention is not impaired. When the step is performed later, it may be removed again after crosslinking, if necessary. The amount of the residual organic solvent is preferably 0.1% by weight or less, and more preferably 0.01% by weight or less.
If necessary, the dispersion can be heated and stirred before the organic solvent is distilled off.
The resulting aqueous dispersion of water-insoluble polymer particles containing the pigment is a dispersion in which the solid content of the polymer containing the pigment is dispersed in water as the main medium. Here, the form of the polymer particles is not particularly limited as long as the particles are formed of at least a pigment and a water-insoluble polymer. For example, the particle form in which the pigment is encapsulated in the polymer, the particle form in which the pigment is uniformly dispersed in the polymer, the particle form in which the pigment is exposed on the polymer particle surface, and the like, and mixtures thereof are also included. .
工程（３）
工程（３）は、工程（２）で得られた顔料を含有する水不溶性ポリマー粒子のポリマーを架橋剤で架橋させて、顔料を含有する架橋ポリマー粒子の水分散体を得る工程である。工程（３）は、水系インクの粘度を低減し、印字濃度を向上させる観点から、行うことが好ましい。
ここで、架橋剤としては、ポリマーの塩生成基と反応する官能基を有する化合物が好ましく、該官能基を分子中に２以上、好ましくは２〜６有する化合物がより好ましい。
この架橋剤は、ポリマーの表面を効率よく架橋する観点から、２５℃の水１００ｇに溶解させたときの溶解量が、好ましくは５０ｇ以下、より好ましくは４０ｇ以下、更に好ましくは３０ｇ以下である。また、架橋剤の分子量は、インクの粘度及び印字濃度の観点から、好ましくは１２０〜２０００、より好ましくは１５０〜１５００、更に好ましい１５０〜１０００である。
Step (3)
Step (3) is a step of obtaining a water dispersion of crosslinked polymer particles containing a pigment by crosslinking the polymer of water-insoluble polymer particles containing the pigment obtained in step (2) with a crosslinking agent. Step (3) is preferably performed from the viewpoint of reducing the viscosity of the water-based ink and improving the printing density.
Here, as a crosslinking agent, the compound which has a functional group which reacts with the salt formation group of a polymer is preferable, and the compound which has this functional group 2 or more in a molecule | numerator, Preferably 2-6 is more preferable.
From the viewpoint of efficiently crosslinking the surface of the polymer, the amount of the crosslinking agent when dissolved in 100 g of water at 25 ° C. is preferably 50 g or less, more preferably 40 g or less, and even more preferably 30 g or less. The molecular weight of the cross-linking agent is preferably 120 to 2000, more preferably 150 to 1500, and still more preferably 150 to 1000 from the viewpoint of ink viscosity and printing density.
（架橋剤）
架橋剤の好適例としては、次の（ａ）〜（ｃ）が挙げられる。
（ａ）分子中に２以上のエポキシ基を有する化合物：例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、グリセリントリグリシジルエーテル、グリセロールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、レゾルシノールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、水添ビスフェノールＡ型ジグリシジルエーテル等のポリグリシジルエーテル。
（ｂ）分子中に２以上のオキサゾリン基を有する化合物：例えば、２，２’−ビス（２−オキサゾリン）、１，３−フェニレンビスオキサゾリン、１，３−ベンゾビスオキサゾリン等のビスオキサゾリン化合物、該化合物と多塩基性カルボン酸とを反応させて得られる末端オキサゾリン基を有する化合物。
（ｃ）分子中に２以上のイソシアネート基を有する化合物：例えば、有機ポリイソシアネート又はイソシアネート基末端プレポリマー。
これらの中では、（ａ）分子中に２以上のエポキシ基を有する化合物が好ましく、特にエチレングリコールジグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテルが好ましい。
(Crosslinking agent)
Preferable examples of the crosslinking agent include the following (a) to (c).
(A) Compound having two or more epoxy groups in the molecule: for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether Polyglycidyl ethers such as trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, hydrogenated bisphenol A type diglycidyl ether.
(B) Compounds having two or more oxazoline groups in the molecule: for example, bisoxazoline compounds such as 2,2′-bis (2-oxazoline), 1,3-phenylenebisoxazoline, 1,3-benzobisoxazoline, A compound having a terminal oxazoline group obtained by reacting the compound with a polybasic carboxylic acid.
(C) Compound having two or more isocyanate groups in the molecule: for example, organic polyisocyanate or isocyanate group-terminated prepolymer.
Among these, (a) a compound having two or more epoxy groups in the molecule is preferable, and ethylene glycol diglycidyl ether and trimethylolpropane polyglycidyl ether are particularly preferable.
架橋剤の使用量は、インク中でのポリマー粒子（Ａ）のインクの粘度の観点から、〔架橋剤／ポリマー〕の重量比で０．１／１００〜５０／１００が好ましく、０．５／１００〜４０／１００がより好ましく、１／１００〜３０／１００が更に好ましく、２／１００〜２５／１００が特に好ましい。
また、架橋剤の使用量は、該ポリマー１ｇ当たりに対して、架橋剤の反応性基のモル数として、０．０１〜１０ｍｍｏｌと反応する量であることが好ましく、０．０５〜５ｍｍｏｌであることがより好ましく、０．１〜２ｍｍｏｌと反応する量であることが更に好ましい。
工程（３）で得られた、架橋ポリマー粒子の水分散体における架橋ポリマーは、架橋ポリマー１ｇ当たり、中和された塩生成基（好ましくはカルボキシ基）を０．５ｍｍｏｌ以上含有することが好ましい。かかる架橋ポリマーは、水分散体中で解離して、塩生成基同士の電荷反発により、顔料を含有する架橋ポリマー粒子の安定性に寄与すると考えられる。
ここで、下記式（３）から求められる架橋ポリマーの架橋率（モル％）は、好ましくは１０〜９０モル％、より好ましくは２０〜８０モル％、更に好ましくは３０〜７０モル％である。架橋率は、架橋剤の使用量と反応性基のモル数、ポリマーの使用量と架橋剤の反応性基と反応できるポリマーの反応性基のモル数から計算で求めることができる。
架橋率（モル％）＝［架橋剤の反応性基のモル数／ポリマーが有する架橋剤と反応し得る反応性基のモル数］×１００ （３）
式（３）において、「架橋剤の反応性基のモル数」とは、使用する架橋剤のモル数に架橋剤１分子中の反応性基の数を乗じたものである。
なお、ポリマーの架橋は、工程（１）で得られた顔料を含有するポリマー粒子の分散体と架橋剤とを混合して行うこともできる。この場合は、該架橋工程で得られた架橋ポリマー粒子の水分散体から、有機溶媒を除去する工程を前記工程（２）と同様に行うことにより、顔料を含有する架橋ポリマー粒子の水分散体を得ることができる。
The amount of the crosslinking agent used is preferably 0.1 / 100 to 50/100 in terms of the weight ratio of [crosslinking agent / polymer] from the viewpoint of the viscosity of the polymer particles (A) in the ink. 100-40 / 100 is more preferable, 1 / 100-30 / 100 is still more preferable, and 2 / 100-25 / 100 is especially preferable.
The amount of the crosslinking agent used is preferably an amount that reacts with 0.01 to 10 mmol as the number of moles of reactive groups of the crosslinking agent per 1 g of the polymer, and is 0.05 to 5 mmol. It is more preferable that the amount reacts with 0.1 to 2 mmol.
The crosslinked polymer in the aqueous dispersion of crosslinked polymer particles obtained in step (3) preferably contains 0.5 mmol or more of neutralized salt-forming groups (preferably carboxy groups) per 1 g of the crosslinked polymer. Such a crosslinked polymer is considered to contribute to the stability of the crosslinked polymer particles containing the pigment by dissociating in the aqueous dispersion and charge repulsion between the salt-forming groups.
Here, the crosslinking rate (mol%) of the crosslinked polymer obtained from the following formula (3) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and still more preferably 30 to 70 mol%. The crosslinking rate can be determined by calculation from the amount of the crosslinking agent used and the number of moles of the reactive group, the amount of polymer used and the number of moles of the reactive group of the polymer that can react with the reactive group of the crosslinking agent.
Crosslinking rate (mol%) = [number of moles of reactive group of crosslinking agent / number of moles of reactive group capable of reacting with crosslinking agent of polymer] × 100 (3)
In the formula (3), “the number of moles of the reactive group of the crosslinking agent” is obtained by multiplying the number of moles of the crosslinking agent to be used by the number of reactive groups in one molecule of the crosslinking agent.
The polymer can be crosslinked by mixing a dispersion of polymer particles containing the pigment obtained in step (1) and a crosslinking agent. In this case, an aqueous dispersion of crosslinked polymer particles containing a pigment is obtained by performing the step of removing the organic solvent from the aqueous dispersion of crosslinked polymer particles obtained in the crosslinking step in the same manner as in the step (2). Can be obtained.
工程（４）
工程（４）は、工程（２）又は（３）で得られた固形分濃度１５重量％以上の水分散体に、電解質を添加し、該水分散体の導電率を〔膜処理前の水分散体の導電率±２５％〕の範囲内に保持しつつ膜処理し、膜処理前における顔料に吸着していない水不溶性ポリマー量の５重量％以上を除去する工程である。
膜処理とは、膜により膜の分画分子量以下の成分と、分画分子量以上の成分に分画する処理をいい、具体的には、分離膜により水分散体をろ過して精製する処理である。この膜処理によって、水分散体中の顔料に吸着していない不安定な水不溶性ポリマーを低減ないし除去した水系顔料分散体を効率的に得ることができる。
膜処理により、導電率が低くなり、導電率が低くなると粘度が上昇する。また、導電率が高くなってもやはり粘度が上昇し、導電率を極端に高くすると凝集が生じる。
そこで、水分散体の導電率を〔膜処理前の水分散体の導電率±２５％〕の範囲内、好ましくは膜処理前の水分散体の導電率±１５％〕の範囲内、より好ましくは膜処理前の水分散体の導電率±１０％〕の範囲内に保持しつつ膜処理する。
Step (4)
In the step (4), an electrolyte is added to the aqueous dispersion having a solid content concentration of 15% by weight or more obtained in the step (2) or (3), and the conductivity of the aqueous dispersion is changed to [water before membrane treatment]. It is a step of removing the 5% by weight or more of the amount of the water-insoluble polymer that is not adsorbed on the pigment before the film treatment while maintaining the film within the range of the conductivity of the dispersion ± 25%].
Membrane treatment is a process of fractionating a membrane with a fractional molecular weight or less and a fractional molecular weight or more with a membrane. Specifically, this is a process of purifying the aqueous dispersion by filtration through a separation membrane. is there. By this membrane treatment, an aqueous pigment dispersion in which unstable water-insoluble polymers not adsorbed on the pigment in the aqueous dispersion are reduced or removed can be efficiently obtained.
By the membrane treatment, the conductivity is lowered, and when the conductivity is lowered, the viscosity is increased. In addition, even when the conductivity is increased, the viscosity also increases, and when the conductivity is extremely increased, aggregation occurs.
Therefore, the electrical conductivity of the aqueous dispersion is preferably within the range of [conductivity of aqueous dispersion before membrane treatment ± 25%], preferably within the range of electrical conductivity of aqueous dispersion before membrane treatment ± 15%]. Is subjected to the film treatment while maintaining it within the range of the conductivity of the aqueous dispersion before the film treatment ± 10%.
本発明においては、水分散体の導電率を前記範囲内に保持するために、電解質を溶液として添加する。添加する電解質液は、膜を透過した膜透過液の導電率に近い導電率を有する電解質液が好ましい。より具体的には、〔膜透過液の導電率±２５％〕の範囲、より好ましくは〔膜透過液の導電率±１５％〕の範囲、より好ましくは〔膜透過液の導電率±１０％〕の範囲の導電率を有する電解質液が好ましい。
電解質液の添加量は、膜処理する前の原料と同量となるまで添加することが好ましく、顔料、水不溶性ポリマー等の種類、量等により異なるが、通常、膜を透過しなかった残液に対して１〜５０重量％、好ましくは５〜４０重量％、より好ましくは１０〜３０重量％である。
電解質は、膜処理を行う前に添加してもよいし、膜処理を行った後に添加してもよい。繰り返し膜処理を行う場合には、膜処理を行った後に電解質を添加し、それを繰り返しながら膜処理を行うことができる。
上記の膜処理により、生産性よく保存安定性の優れた水系顔料分散体を製造する観点から、膜処理前における顔料に吸着していない水不溶性ポリマー量の５重量％以上、好ましくは１０重量％以上、より好ましくは２０重量％以上、最も好ましくは１００重量％除去する。
In the present invention, an electrolyte is added as a solution in order to maintain the conductivity of the aqueous dispersion within the above range. The electrolyte solution to be added is preferably an electrolyte solution having a conductivity close to the conductivity of the membrane permeate that has passed through the membrane. More specifically, a range of [conductivity of membrane permeate ± 25%], more preferably a range of [conductivity of membrane permeate ± 15%], more preferably [conductivity of membrane permeate ± 10%]. An electrolyte solution having a conductivity in the range of
The amount of the electrolyte solution added is preferably the same as the amount of the raw material before membrane treatment, and it varies depending on the type and amount of pigment, water-insoluble polymer, etc., but usually the residual solution that did not permeate the membrane 1 to 50% by weight, preferably 5 to 40% by weight, and more preferably 10 to 30% by weight.
The electrolyte may be added before the membrane treatment or after the membrane treatment. When the film treatment is repeatedly performed, the electrolyte can be added after the film treatment, and the film treatment can be performed while repeating the treatment.
From the viewpoint of producing a water-based pigment dispersion excellent in productivity and storage stability by the above membrane treatment, 5% by weight or more, preferably 10% by weight, of the amount of water-insoluble polymer not adsorbed on the pigment before membrane treatment. More preferably, 20% by weight or more, most preferably 100% by weight is removed.
膜処理される水分散体の固形分濃度が高いほうが、膜処理効率が高くなる。その観点から、水分散体の固形分濃度は１５重量％以上であり、分散体粘度の観点から４０重量％以下が好ましく、２０〜３５重量％がより好ましい。
膜処理は、溶剤除去を行う前の水分散体を対象にして行ってもよい。その際には、膜処理後に溶剤除去を行えばよく、更に架橋処理を行ってもよい。また、溶剤除去を行った水分散体を更に膜処理してもよい。
また、架橋処理を行う前の水分散体を膜処理してもよい。その際には、膜処理後に架橋処理を行ってもよく、また架橋処理を行った後に再び膜処理を行ってもよい。架橋処理を行うと、顔料に吸着した水不溶性ポリマーの脱離が生じる割合が低下するので、架橋処理を行った後に膜処理を行うことが好ましい。
膜処理の回数に特に制限はなく、異なる種類の膜を組み合わせて行うこともできる。
The higher the solid content concentration of the aqueous dispersion subjected to membrane treatment, the higher the membrane treatment efficiency. From this viewpoint, the solid content concentration of the aqueous dispersion is 15% by weight or more, preferably 40% by weight or less, more preferably 20 to 35% by weight from the viewpoint of dispersion viscosity.
The membrane treatment may be performed on an aqueous dispersion before solvent removal. In that case, the solvent may be removed after the film treatment, and a crosslinking treatment may be further performed. Further, the aqueous dispersion from which the solvent has been removed may be further subjected to membrane treatment.
Moreover, you may membrane-treat the aqueous dispersion before performing a crosslinking process. In that case, the crosslinking treatment may be performed after the film treatment, or the film treatment may be performed again after the crosslinking treatment. When the crosslinking treatment is performed, the rate at which the water-insoluble polymer adsorbed on the pigment is eliminated decreases. Therefore, it is preferable to perform the membrane treatment after the crosslinking treatment.
There is no restriction | limiting in particular in the frequency | count of a film | membrane process, It can also carry out combining a different kind of film | membrane.
膜処理の方式は特に制限はなく、全量ろ過方式でもクロスフローろ過方式でもよいが、供給する分散体中の懸濁物質等が膜面に堆積するのを防止等の観点から、クルスフローろ過方式が好ましい。ろ過膜としては、精密ろ過膜（ＭＦ膜、ろ過精度：約０．１μｍ）、限外ろ過膜（ＵＦ膜、ろ過精度：約１０ｎｍ）、ナノフィルター（ＮＦ膜、ろ過精度：約１ｎｍ）、逆浸透膜（ＲＯ膜、ろ過精度：約０．１ｎｍ）等を使用することができる。ろ過膜の孔径は、好ましくは１〜５０ｎｍ、より好ましくは２〜３０ｎｍ、更に好ましくは３〜２０ｎｍである。
用いられるろ過膜としては、有機溶媒により劣化しないものであれば特に限定されない。例えば、セルロース膜、３０４及び３１６ステンレススチール膜、漂白コットン膜、ポリスルホン（ＰＳ）膜、ポリプロピレン（ＰＰ）膜、ポリエーテルサルフォン（ＰＥＳ）膜、ポリエチレンテレフタレート（ＰＥＴ）膜、ポリフッ化ビニルデン（ＰＶＤＦ）膜、ポリカーボネイト（ＰＣＴＥ）膜、ポリ４フッ化エチレン（ＰＴＦＥ）等の各種の材料を主原料とするろ過膜が挙げられる。これらの中でも、ポリスルホン（ＰＳ）膜、ポリ４フッ化エチレン（ＰＴＦＥ）膜、ポリエーテルサルフォン（ＰＥＳ）膜、ポリエチレンテレフタレート（ＰＥＴ）膜、ポリフッ化ビニルデン膜及びポリカーボネイト（ＰＣＴＥ）膜が好ましく、ポリエーテルサルフォン（ＰＥＳ）膜が更に好ましい。
The membrane treatment method is not particularly limited and may be a total filtration method or a cross flow filtration method. However, from the viewpoint of preventing the suspended substances in the supplied dispersion from accumulating on the membrane surface, the Cruz flow filtration method. Is preferred. As filtration membrane, microfiltration membrane (MF membrane, filtration accuracy: about 0.1 μm), ultrafiltration membrane (UF membrane, filtration accuracy: about 10 nm), nanofilter (NF membrane, filtration accuracy: about 1 nm), reverse An osmotic membrane (RO membrane, filtration accuracy: about 0.1 nm) or the like can be used. The pore diameter of the filtration membrane is preferably 1 to 50 nm, more preferably 2 to 30 nm, and still more preferably 3 to 20 nm.
The filtration membrane used is not particularly limited as long as it does not deteriorate with an organic solvent. For example, cellulose film, 304 and 316 stainless steel film, bleached cotton film, polysulfone (PS) film, polypropylene (PP) film, polyethersulfone (PES) film, polyethylene terephthalate (PET) film, polyvinylidene fluoride (PVDF) Examples thereof include filtration membranes mainly composed of various materials such as a membrane, a polycarbonate (PCTE) membrane, and polytetrafluoroethylene (PTFE). Among these, a polysulfone (PS) film, a polytetrafluoroethylene (PTFE) film, a polyethersulfone (PES) film, a polyethylene terephthalate (PET) film, a polyvinylidene fluoride film, and a polycarbonate (PCTE) film are preferable. Ether sulfone (PES) membranes are more preferred.
精密ろ過膜としては、ろ材の内部で異物を捕捉するデプスタイプ（厚みろ過型）や、ろ材の表面で異物を捕捉するサーフェスタイプ（面ろ過型）が挙げられる。精密ろ過膜の市販品としては、サーフェスタイプについては、エポセル（株式会社日本触媒製）、ポールセル（日本ポール株式会社製）等のセルロース膜、リジメッシュ（日本ポール株式会社製）等の３０４ステンレススチール膜、ミクロピュア（ロキテクノ株式会社製）等のポリプロピレン膜、サスピュア（ロキテクノ株式会社製）等の３１６ステンレススチール膜、ＴＣＰ、ＴＣＰＥ、ＴＣ（東洋濾紙株式会社製）等のポリプロピレン膜が挙げられる。また、デプスタイプについては、プロファイル（日本ポール株式会社製）等のポリプロピレン膜、マイクロシリア（株式会社ロキテクノ製）等の漂白コットン、ダイア、ダイアII（Ｐ）、ダイアII（Ｃ）、ピュアロン、シリアクリーン、ＳＬ、ＳＬＮ、グラスロン等のポリプロピレン膜、ＴＣＰＤ、ＴＣＷ−ＰＰ、ＴＣＷ−ＣＳ、ＴＣＷ−ＥＰ（東洋濾紙株式会社製）等のポリプロピレン膜が挙げられる。 Examples of the microfiltration membrane include a depth type (thickness filtration type) that traps foreign substances inside the filter medium, and a surface type (surface filtration type) that traps foreign substances on the surface of the filter medium. Commercially available microfiltration membranes include cellulose membranes such as Epocell (manufactured by Nippon Shokubai Co., Ltd.) and Pole Cell (manufactured by Nippon Pole Co., Ltd.), and 304 stainless steel membranes such as rigesh mesh (manufactured by Nippon Pole Co., Ltd.). And polypropylene films such as micropure (manufactured by Loki Techno Co., Ltd.), 316 stainless steel films such as Sus Pure (manufactured by Loki Techno Co., Ltd.), and polypropylene films such as TCP, TCPE, TC (manufactured by Toyo Filter Paper Co., Ltd.). For depth types, polypropylene membranes such as profiles (manufactured by Nippon Pole Co., Ltd.), bleached cotton such as micro-Syria (manufactured by Loki Techno Co., Ltd.), Dia, Dia II (P), Dia II (C), Purelon, Syria Examples include polypropylene films such as clean, SL, SLN, and glassron, and polypropylene films such as TCPD, TCW-PP, TCW-CS, and TCW-EP (manufactured by Toyo Roshi Kaisha, Ltd.).
限外ろ過膜、ナノフィルター、逆浸透膜の市販品としては、例えば、ＮＴＵシリーズの商品名：２０２０、２１２０、３５２０、３１５０、３００６、３０５０、３２５０、３５５０、４２０８、４２２０、ＮＦＳシリーズの商品名：１００、１０１、１０３、ＮＴＭ−９００２、ＲＳ−３０（日東電工株式会社製）等のポリスルホン膜、ＡＩＰ−００１３、ＡＣＰ−００１３、ＡＣＰ−００５３、ＡＨＰ−００１３、ＡＩＶシリーズの商品名：３０１０、５０１０、ＡＣＶシリーズの商品名：３０１０、３０５０、５０１０、５０５０、ＳＩＷ−３０５４、ＳＥＰ−００１３、ＳＡＰ−００１３、ＳＩＰ−００１３、ＳＬＰ−００５３、マイクローザ（旭化成工業株式会社製）等のポリフッ化ビニルデン膜、ミニクロス、クロスフロモジュール（東洋紡績株式会社製）等のポリプロピレン膜が挙げられる。
膜の形状としては、中空糸状型、管型、平板型、モノリス型等が挙げられ、分散体を流す方式としては、内圧ろ過方式でも外圧ろ過方式でもよい。
上記の中では、限外ろ過膜を用いたクルスフローろ過方式がより好ましい。また、有機溶媒を加えながらろ過する透析ろ過（ダイアフィルトレーション）方式も好ましい。
Examples of commercially available ultrafiltration membranes, nanofilters, and reverse osmosis membranes include NTU series product names: 2020, 2120, 3520, 3150, 3006, 3050, 3250, 3550, 4208, 4220, and NFS series. : 100, 101, 103, NTM-9002, RS-30 (manufactured by Nitto Denko Corporation), etc., polysulfone membranes, AIP-0013, ACP-0013, ACP-0053, AHP-0013, AIV series product names: 3010, 5010, ACV series product names: 3010, 3050, 5010, 5050, SIW-3054, SEP-0013, SAP-0013, SIP-0013, SLP-0053, Microza (made by Asahi Kasei Kogyo Co., Ltd.), etc. Membrane, mini cloth, cross flow module Polypropylene film, such as Le (manufactured by Toyobo Co., Ltd.) and the like.
Examples of the shape of the membrane include a hollow fiber type, a tube type, a flat plate type, a monolith type, and the like, and the method of flowing the dispersion may be an internal pressure filtration method or an external pressure filtration method.
Among the above, a crus flow filtration method using an ultrafiltration membrane is more preferable. Further, a diafiltration method that performs filtration while adding an organic solvent is also preferable.
クルスフローろ過方式で、膜処理を施すと、低分子物質である電解質は、分画分子量より小さい成分に分配され、膜を透過した透過液中に取り込まれる。一方、顔料を含む分画分子量以上の成分は残液（濃縮液）中に取り込まれるため、残液（濃縮液）の濃度は高くなり、導電率は減少する。導電率の減少した成分を更に膜処理すると、徐々に粘度が上昇し、最終的には膜処理を実質的に行えなくなるまで粘度が上昇する。
そこで、クロスフローろ過膜処理において、膜透過液と残液に分離し、系外に取り出された膜透過液に相当する量の電解質液を残液に添加して、水分散体の導電率を前記範囲内に保持しつつ膜処理すると膜処理を継続して行うことができる。その結果、水分散体中の顔料に吸着していない不安定な水不溶性ポリマーを低減ないし除去した水系顔料分散体を生産性よく、効率的に得ることができる。
ここで、前記のとおり、添加する電解質液は、膜を透過した膜透過液の導電率に近い導電率を有する電解質液が好ましく、電解質液の添加量は、膜処理する前の原料量と同量とするまで追加ことが好ましい。
When membrane treatment is performed by the Cruz flow filtration method, the electrolyte, which is a low molecular weight substance, is distributed into components smaller than the fractional molecular weight and taken into the permeate that has permeated the membrane. On the other hand, since components having a molecular weight higher than the fractional molecular weight including the pigment are taken into the residual liquid (concentrated liquid), the concentration of the residual liquid (concentrated liquid) increases and the conductivity decreases. If the component having reduced conductivity is further subjected to film treatment, the viscosity gradually increases, and finally the viscosity increases until the film treatment cannot be substantially performed.
Therefore, in the cross-flow filtration membrane treatment, the membrane permeate and the residual liquid are separated, and an electrolyte solution in an amount corresponding to the membrane permeate taken out of the system is added to the residual liquid, so that the conductivity of the aqueous dispersion is increased. If the film treatment is carried out while keeping within the above range, the film treatment can be continued. As a result, an aqueous pigment dispersion in which unstable water-insoluble polymers not adsorbed on the pigment in the aqueous dispersion are reduced or removed can be efficiently obtained with high productivity.
Here, as described above, the electrolyte solution to be added is preferably an electrolyte solution having a conductivity close to the conductivity of the membrane permeation solution that has passed through the membrane, and the amount of the electrolyte solution added is the same as the amount of the raw material before the membrane treatment. It is preferable to add until the amount.
（電解質）
本発明に用いられる電解質は、水分散体の導電率を一定に保つ目的で添加される。電解質としては、水分散体中で陽イオン及び陰イオンに電離し、導電性を示す化合物であれば特に制限はなく、固体であっても、水溶液であってもよい。
電解質の電離性の強さは、導電率を測定することにより知ることができる。導電率は試料中の電気の流れやすさを示す指標であり、定法により測定することができる。
電解質から電離された陽イオンとしては、Ｈ+、Ｎａ+、Ｌｉ+、Ｋ+、Ｃａ2+、Ｍｇ2+、ＮＨ4+、ＣＨ3ＮＨ3+、（ＣＨ3）2ＮＨ2+、（ＣＨ3）3ＮＨ+、（ＣＨ3）4Ｎ+等が挙げられ、また、陰イオンとしては、ＯＨ-、Ｃｌ-、Ｂｒ-、Ｆ-、Ｉ-、ＭｎＯ4-、ＣｌＯ4-、ＰＯ4 3-、ＳＯ4 2-、ＮＯ3-等が挙げられる。
(Electrolytes)
The electrolyte used in the present invention is added for the purpose of keeping the conductivity of the aqueous dispersion constant. The electrolyte is not particularly limited as long as it is a compound that is ionized into a cation and an anion in a water dispersion and exhibits conductivity, and may be a solid or an aqueous solution.
The ionizing strength of the electrolyte can be known by measuring the conductivity. The conductivity is an index indicating the ease of electricity flow in the sample and can be measured by a conventional method.
Cations ionized from the electrolyte include H + , Na + , Li + , K + , Ca 2+ , Mg 2+ , NH 4+ , CH 3 NH 3+ , (CH 3 ) 2 NH 2+ , ( CH 3 ) 3 NH + , (CH 3 ) 4 N + and the like, and the anions include OH − , Cl − , Br − , F − , I − , MnO 4− , ClO 4− , PO. 4 3− , SO 4 2− , NO 3− and the like.
電解質としては、酸、塩基、無機塩、有機電解質化合物が用いられる。
酸としては、塩酸、硝酸、硫酸等の無機酸が挙げられ、塩基としては、水酸化リチウム、水酸化カリウム、水酸化ナトリウム、アンモニア等の無機塩基、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジメチルアミン、トリメチルアミン等のアミンが挙げられる。
無機塩としては、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩等が挙げられる。
アルカリ金属塩としては、塩化リチウム、硝酸リチウム、硫酸リチウム、炭酸リチウム、過塩素酸リチウム、塩化ナトリウム、炭酸水素ナトリウム、硝酸ナトリウム、炭酸ナトリウム、硫酸ナトリウム、硫酸ナトリウム、亜硫酸ナトリウム、過塩素酸ナトリウム、硝酸カリウム、硫酸カリウム、炭酸カリウム、塩化カリウム、臭化カリウム等が挙げられる。アルカリ土類金属塩としては、硫酸カルシウム、硝酸カルシウム、塩化カルシウム、クロム酸カルシウム、硫酸マグネシウム等が挙げられる。
アンモニウム塩としては、塩化アンモニウム、硝酸アンモニウム、硫酸アンモニウム、酢酸アンモニウム等が挙げられる。その他の無機塩としては、硝酸銀、硫酸銀、硝酸銅、硫酸銅、塩化銅、硝酸亜鉛、硫酸亜鉛、硝酸アルミニウム、硫酸アルミニウム等が挙げられる。
As the electrolyte, an acid, a base, an inorganic salt, or an organic electrolyte compound is used.
Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid. Examples of the base include inorganic bases such as lithium hydroxide, potassium hydroxide, sodium hydroxide, and ammonia, monoethanolamine, diethanolamine, triethanolamine, and dimethyl. Examples include amines and trimethylamine.
Examples of inorganic salts include alkali metal salts, alkaline earth metal salts, ammonium salts and the like.
Alkali metal salts include lithium chloride, lithium nitrate, lithium sulfate, lithium carbonate, lithium perchlorate, sodium chloride, sodium bicarbonate, sodium nitrate, sodium carbonate, sodium sulfate, sodium sulfate, sodium sulfite, sodium perchlorate, Examples include potassium nitrate, potassium sulfate, potassium carbonate, potassium chloride, and potassium bromide. Examples of the alkaline earth metal salt include calcium sulfate, calcium nitrate, calcium chloride, calcium chromate, magnesium sulfate and the like.
Examples of ammonium salts include ammonium chloride, ammonium nitrate, ammonium sulfate, and ammonium acetate. Examples of other inorganic salts include silver nitrate, silver sulfate, copper nitrate, copper sulfate, copper chloride, zinc nitrate, zinc sulfate, aluminum nitrate, and aluminum sulfate.
有機電解質化合物としては、安息香酸ナトリウム、フタル酸ナトリウム、フマル酸ナトリウム、マレイン酸ナトリウム、酪酸ナトリウム、酢酸カリウム、クエン酸カリウム等の有機酸塩、蟻酸アンモニウム、シュウ酸アンモニウム等の有機アンモニウム塩が挙げられる。
これらの中では、強電解質が好ましく、無機塩及び／又は無機塩基がより好ましく、アルカリ金属塩及び／又はアルカリ土類金属塩が更に好ましく、アルカリ金属塩が更に好ましく、炭酸水素ナトリウム、水酸化ナトリウムが特に好ましい。
上記の電解質は、単独で又は２種以上を組み合わせて用いることができる。
Examples of the organic electrolyte compound include organic acid salts such as sodium benzoate, sodium phthalate, sodium fumarate, sodium maleate, sodium butyrate, potassium acetate and potassium citrate, and organic ammonium salts such as ammonium formate and ammonium oxalate. It is done.
Among these, strong electrolytes are preferred, inorganic salts and / or inorganic bases are more preferred, alkali metal salts and / or alkaline earth metal salts are more preferred, alkali metal salts are still more preferred, sodium bicarbonate, sodium hydroxide Is particularly preferred.
Said electrolyte can be used individually or in combination of 2 or more types.
［インクジェット記録用水分散体］
前記の製造方法等によって得られた本発明の水系顔料分散体は、保存時には、乾燥防止のために、水溶性有機溶媒や保湿剤を含有させることが好ましく、そのまま水系インクとして用いることもできる。また、インクジェット記録用水系インクに通常用いられる湿潤剤、浸透剤、分散剤、粘度調整剤、消泡剤、防黴剤、防錆剤等を添加してもよい。
本発明の水系顔料分散体中の各成分の含有量は、下記のとおりである。
水不溶性ポリマー粒子に含まれる顔料の含有量は、水系顔料分散体の印字濃度を高める観点から、水系顔料分散体中で、好ましくは２〜３５重量％、より好ましくは３〜３０重量％、更に好ましくは５〜２５重量％である。
水の含有量は、好ましくは２０〜９０重量％，より好ましくは３０〜８０重量％、更に好ましくは４０〜７０重量％である。
水系顔料分散体の好ましい表面張力（２０℃）は、３０〜７０ｍＮ／ｍ、より好ましくは３５〜６５ｍＮ／ｍである。
水系顔料分散体の２０重量％（固形分濃度）の粘度（２０℃）は、好ましくは１〜１２ｍＰａ・ｓ、より好ましくは１〜９ｍＰａ・ｓ、より好ましくは２〜６ｍＰａ・ｓ、更に好ましくは２〜５ｍＰａ・ｓである。この水系顔料分散体の不揮発成分は、通常、印字濃度、吐出安定性等の観点から、１〜３０重量％、更に３〜２５重量％となるように調整することが好ましい。
本発明の製造方法によって得られた水系顔料分散体は、インクジェット記録用の水系顔料分散体及び水系インクに好適に使用しうるものとなる。
本発明の水系インクを適用しうるインクジェット記録装置は特に制限されないが、特にサーマル及びピエゾ方式のオンデマンドインクジェットプリンターに好適である。また、高速印字が可能なプリンターに適しており、例えば３〜１５０枚／分、好ましくは５〜１００枚／分、より好ましくは１０〜１００枚／分の印字速度で印刷しうるプリンターに好適に使用することができる。
[Water dispersion for inkjet recording]
The water-based pigment dispersion of the present invention obtained by the above-described production method or the like preferably contains a water-soluble organic solvent or a humectant to prevent drying during storage, and can be used as it is as a water-based ink. In addition, wetting agents, penetrating agents, dispersants, viscosity modifiers, antifoaming agents, antifungal agents, rustproofing agents, and the like that are commonly used in water-based inks for inkjet recording may be added.
The content of each component in the aqueous pigment dispersion of the present invention is as follows.
The content of the pigment contained in the water-insoluble polymer particles is preferably 2 to 35% by weight, more preferably 3 to 30% by weight in the aqueous pigment dispersion from the viewpoint of increasing the printing density of the aqueous pigment dispersion. Preferably it is 5 to 25% by weight.
The water content is preferably 20 to 90% by weight, more preferably 30 to 80% by weight, and still more preferably 40 to 70% by weight.
The surface tension (20 ° C.) of the aqueous pigment dispersion is preferably 30 to 70 mN / m, more preferably 35 to 65 mN / m.
The viscosity (20 ° C.) of 20% by weight (solid content concentration) of the aqueous pigment dispersion is preferably 1 to 12 mPa · s, more preferably 1 to 9 mPa · s, more preferably 2 to 6 mPa · s, and still more preferably. 2 to 5 mPa · s. In general, the non-volatile component of the water-based pigment dispersion is preferably adjusted to 1 to 30% by weight, and more preferably 3 to 25% by weight, from the viewpoints of print density and ejection stability.
The aqueous pigment dispersion obtained by the production method of the present invention can be suitably used for an aqueous pigment dispersion for inkjet recording and an aqueous ink.
The ink jet recording apparatus to which the water-based ink of the present invention can be applied is not particularly limited, but is particularly suitable for thermal and piezo on-demand ink jet printers. Further, it is suitable for a printer capable of high-speed printing, for example, 3 to 150 sheets / minute, preferably 5 to 100 sheets / minute, more preferably 10 to 100 sheets / minute. Can be used.
以下の製造例、実施例及び比較例において、「部」及び「％」は特記しない限り「重量部」及び「重量％」である。
なお、ポリマーの重量平均分子量、導電率、水不溶性ポリマーの除去率、インクの保存安定性の測定、評価は以下の方法により行った。
（１）ポリマーの重量平均分子量
溶媒として、６０ｍｍｏｌ／Ｌのリン酸と５０ｍｍｏｌ／Ｌのリチウムブロマイドを含有するＮ，Ｎ−ジメチルホルムアミドを用いたゲルクロマトグラフィー法〔東ソー株式会社製ＧＰＣ装置（ＨＬＣ−８１２０ＧＰＣ）、東ソー株式会社製カラム（ＴＳＫ-ＧＥＬ、α-Ｍ×２本）、流速：１ｍＬ／ｍｉｎ〕により、標準物質としてポリスチレンを用いて測定した。
（２）導電率
導電率計（株式会社堀場製作所製、ＥＳ−５１）を用いて、２０℃で水系顔料分散体の導電率（ｍＳ／ｃｍ）を測定した。
（３）水不溶性ポリマーの除去率
顔料に吸着していない水不溶性ポリマーの除去率は、膜処理前後における顔料に吸着していない水不溶性ポリマーの量から下記式を用いて測定した。
水不溶性ポリマーの除去率（％）＝（（〔膜処理前の顔料に吸着していない水不溶性ポリマーの量〕−〔膜処理後の顔料に吸着していない水不溶性ポリマーの量〕）／〔膜処理前の顔料に吸着していない水不溶性ポリマーの量〕）×１００
ここで、顔料に吸着していない水不溶性ポリマーの量は以下のようにして求めた。水系の顔料分散体を超遠心分離装置（日立工機株式会社製、ＣＰ５６Ｇ）を用い、３０，０００ｒｐｍ×３時間（２０℃）の条件で超遠心分離し、得られた上澄み液の固形分量を下記固形分の測定方法によって求め、顔料に吸着していない水不溶性ポリマー量とした。
上澄み液の固形分量の測定方法は、上澄み液１ｇと硫酸ナトリウム（芒硝）１０ｇとを均一に混合し、蒸発皿１０．５ｃｍ2に均一に広げて、乾燥機で１０５℃、２時間、−０．０７ＭＰａで減圧乾燥させる。固形分量（重量％）は、（乾燥後の上澄み液の重量／乾燥前の上澄み液の重量）×１００として求めることができる。
（４）インクの保存安定性
得られたインクをガラス製密閉容器に充填し、７０℃で１週間保存後の粘度をＥ型粘度計（東機産業株式会社製、ＲＥ８０Ｌ）を用いて２０℃で測定し、下記式より粘度変化率を求め、保存安定性を評価した。
保存安定性（粘度変化率）（％）＝（（〔保存後の粘度〕−〔保存前の粘度〕）／〔保存前の粘度〕）×１００
保存安定性（粘度変化率）が１００％に近い方が良好なインクである。
In the following production examples, examples and comparative examples, “parts” and “%” are “parts by weight” and “% by weight” unless otherwise specified.
The weight average molecular weight of the polymer, the electrical conductivity, the removal rate of the water-insoluble polymer, and the storage stability of the ink were measured and evaluated by the following methods.
(1) Weight average molecular weight of polymer Gel chromatography using N, N-dimethylformamide containing 60 mmol / L phosphoric acid and 50 mmol / L lithium bromide as a solvent [GPC apparatus (HLC- 8120GPC), a column manufactured by Tosoh Corporation (TSK-GEL, α-M × 2), flow rate: 1 mL / min], using polystyrene as a standard substance.
(2) Conductivity The conductivity (mS / cm) of the aqueous pigment dispersion was measured at 20 ° C. using a conductivity meter (manufactured by Horiba, Ltd., ES-51).
(3) Removal rate of water-insoluble polymer The removal rate of the water-insoluble polymer not adsorbed on the pigment was measured using the following formula from the amount of the water-insoluble polymer not adsorbed on the pigment before and after the membrane treatment.
Removal rate of water-insoluble polymer (%) = (([Amount of water-insoluble polymer not adsorbed on pigment before membrane treatment] − [Amount of water-insoluble polymer not adsorbed on pigment after membrane treatment]) / [ Amount of water-insoluble polymer not adsorbed on pigment before membrane treatment]) × 100
Here, the amount of the water-insoluble polymer not adsorbed on the pigment was determined as follows. The aqueous pigment dispersion was ultracentrifuged using an ultracentrifuge (CP56G, manufactured by Hitachi Koki Co., Ltd.) under the condition of 30,000 rpm × 3 hours (20 ° C.), and the solid content of the resulting supernatant was determined. The amount of water-insoluble polymer not adsorbed on the pigment was determined by the following solid content measurement method.
The method for measuring the solid content of the supernatant liquid is to uniformly mix 1 g of the supernatant liquid and 10 g of sodium sulfate (sodium salt), spread it uniformly on an evaporating dish 10.5 cm 2 , and use a dryer at 105 ° C. for 2 hours, −0 Dry under reduced pressure at 0.07 MPa. The solid content (% by weight) can be determined as (weight of supernatant after drying / weight of supernatant before drying) × 100.
(4) Storage stability of ink The obtained ink was filled in a glass sealed container, and the viscosity after storage at 70 ° C. for 1 week was measured at 20 ° C. using an E-type viscometer (RE80L manufactured by Toki Sangyo Co., Ltd.) The viscosity change rate was obtained from the following formula, and the storage stability was evaluated.
Storage stability (Viscosity change rate) (%) = (([viscosity after storage] − [viscosity before storage]) / [viscosity before storage]) × 100
A storage ink (viscosity change rate) closer to 100% is a better ink.
製造例１
反応容器内に、メチルエチルケトン８．２部、重合連鎖移動剤（２-メルカプトエタノール）０．０３部、及び表1に示すモノマー混合物２００部のうちの１０％を入れて混合し、窒素ガス置換を十分に行い、混合溶液を得た。
一方、滴下ロートに、表1のモノマー混合物の残りの９０％を仕込み、重合連鎖移動剤（２−メルカプトエタノール）０．２８部、メチルエチルケトン７３．６部及び２，２'-アゾビス（２，４−ジメチルバレロニトリル）１．８部を入れて混合し、十分に窒素ガス置換を行い、混合液を得た。
窒素雰囲気下、反応容器内の混合液を攪拌しながら７５℃まで昇温し、滴下ロート中の混合溶液を５時間かけて滴下した。滴下終了から７５℃で２時間経過後、２，２'−アゾビス（２，４−ジメチルバレロニトリル）１．６部をメチルエチルケトン２１．８部に溶解した溶液を加え、更に７５℃で２時間、８０℃で２時間熟成させ、ポリマー溶液を得た。
得られたポリマーの重量平均分子量を測定した結果を表１に示す。
Production Example 1
In a reaction vessel, 8.2 parts of methyl ethyl ketone, 0.03 part of a polymerization chain transfer agent (2-mercaptoethanol) and 10% of 200 parts of the monomer mixture shown in Table 1 were mixed and mixed with nitrogen gas. This was carried out sufficiently to obtain a mixed solution.
Meanwhile, the remaining 90% of the monomer mixture shown in Table 1 was charged into the dropping funnel, and 0.28 part of a polymerization chain transfer agent (2-mercaptoethanol), 73.6 parts of methyl ethyl ketone and 2,2′-azobis (2,4 -Dimethylvaleronitrile) 1.8 parts was mixed and nitrogen gas substitution was performed sufficiently to obtain a mixed solution.
Under a nitrogen atmosphere, the temperature of the mixed solution in the reaction vessel was increased to 75 ° C. while stirring, and the mixed solution in the dropping funnel was dropped over 5 hours. After 2 hours at 75 ° C. from the end of dropping, a solution in which 1.6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 21.8 parts of methyl ethyl ketone was added, and further at 75 ° C. for 2 hours, The polymer solution was obtained by aging at 80 ° C. for 2 hours.
The results of measuring the weight average molecular weight of the obtained polymer are shown in Table 1.
実施例１
（１）顔料を含有する架橋ポリマー粒子の水分散体の製造
製造例１で得られた水不溶性ポリマーのメチルエチルケトン溶液（固形分濃度を５０％に調整したもの）３５．３部、メチルエチルケトン６０部、水酸化ナトリウム水溶液（和光純薬工業株式会社製、滴定用標準液：５Ｎ）７部、イオン交換水２５０部を、ガラス製容器に計量し、高速攪拌分散機（プライミクス株式会社製、商品名：Ｔ．Ｋ．ロボミックス＋Ｔ．Ｋ．ホモディスパー２．５型）を用い、１５００ｒｐｍで１５分間混合した。
得られた混合物に、マゼンタ顔料（Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、大日精化工業株式会社製、商品名：クロモファインレッド）１００部を添加し、８０００ｒｐｍで６０分間攪拌した。得られた混合物を更に、マイクロフルイダイザー（マイクロフルイディクス社製、商品名：ＭＦ−１４０Ｋ）を用いて、２００ＭＰａで１９パスで高圧分散処理し、顔料を含有する水不溶性ポリマー粒子の分散体を得た。
得られた分散体を減圧下、６０℃でメチルエチルケトンを実質的に除去し、更に一部の水を除去することにより濃縮し、固形分濃度が３５％の顔料を含有する水不溶性ポリマー粒子を含む水分散体を得た。
得られた水分散体４００ｇに、架橋率が５４モル％となるように架橋剤（ナガセケムテックス株式会社製、商品名：デナコールＥＸ３２１Ｌ、エポキシ当量１２９）を４．４５ｇ及び水を加え、９０℃下で１時間攪拌した。攪拌後、冷却し、５．０μｍのフィルター（アセチルセルロース膜、外径：２．５ｃｍ、富士フィルム株式会社製）を用いて濾過し、顔料を含有する架橋ポリマー粒子の水分散体を得た。得られた水分散体の固形分濃度は３０％、導電率は２．１６ｍＳ／ｃｍ、粘度は７．１３ｍＰａ・ｓであった。
（２）水系顔料分散体の製造（膜処理）
上記（１）で得られた顔料を含有する架橋ポリマー粒子の水分散体４００ｇを限外ろ過膜装置（ミリポア社製、ペリコンII、バイオマックス、Ｖスクリーン、材質：ＰＥＳ、分画分子量５００ｋＤ、膜面積０．１ｍ2）を用いて、全量ろ過した。ろ膜を透過しなかった液（濃縮液）量は３６３ｇであり、その導電率は２．００ｍＳ／ｃｍ、固形分濃度は３３％であった。
別途、導電率が２．２０ｍＳ／ｃｍとなるように炭酸水素ナトリウム水溶液を調整し、膜透過液に相当する量として３７ｇをろ膜を透過しなかった液（濃縮液）に添加して混合したが、増粘は認められなかった。
上記ろ過処理を繰り返して、合計２５パス処理を行った。各パス回数における水不溶性ポリマーの除去率は、１パス後：除去率０％、３パス後：除去率４％、６パス後：除去率７％、９パス後：除去率１０％、１５パス後：除去率１５％、２５パス後：除去率２４％であった。
膜処理２５パス後に得られた固形分濃度３３％の水系顔料分散体を、イオン交換水を用いて３０％に調整した水系顔料分散体の粘度は７．２８ｍＰａ・ｓ、その導電率は２．１１ｍＳ／ｃｍであり、導電率は膜処理前の９７．７％であった。
Example 1
(1) Production of aqueous dispersion of crosslinked polymer particles containing pigment 35.3 parts of a methyl ethyl ketone solution of water-insoluble polymer obtained in Production Example 1 (solid content adjusted to 50%), 60 parts of methyl ethyl ketone, A sodium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd., standard solution for titration: 5N) and 250 parts of ion-exchanged water were weighed into a glass container, and a high-speed stirring disperser (manufactured by Primics Co., Ltd., trade name: TK Robomix + TK homodisper type 2.5) and mixed at 1500 rpm for 15 minutes.
To the obtained mixture, 100 parts of magenta pigment (Pigment Red 122, manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Chromofine Red) was added and stirred at 8000 rpm for 60 minutes. The obtained mixture was further subjected to high-pressure dispersion treatment at 200 MPa and 19 passes using a microfluidizer (trade name: MF-140K, manufactured by Microfluidics Co., Ltd.) to obtain a dispersion of water-insoluble polymer particles containing a pigment. Obtained.
The resulting dispersion is concentrated by substantially removing methyl ethyl ketone at 60 ° C. under reduced pressure and further removing a part of water, and contains water-insoluble polymer particles containing a pigment having a solid content concentration of 35%. An aqueous dispersion was obtained.
To the obtained aqueous dispersion 400 g, 4.45 g of a crosslinking agent (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX321L, epoxy equivalent 129) and water were added so that the crosslinking rate was 54 mol%, and 90 ° C. Stir for 1 hour. After stirring, the mixture was cooled and filtered using a 5.0 μm filter (acetylcellulose membrane, outer diameter: 2.5 cm, manufactured by Fuji Film Co., Ltd.) to obtain an aqueous dispersion of crosslinked polymer particles containing a pigment. The obtained aqueous dispersion had a solid content concentration of 30%, an electric conductivity of 2.16 mS / cm, and a viscosity of 7.13 mPa · s.
(2) Production of aqueous pigment dispersion (film treatment)
400 g of an aqueous dispersion of crosslinked polymer particles containing the pigment obtained in the above (1) was converted into an ultrafiltration membrane device (Millipore, Pericon II, Biomax, V screen, material: PES, molecular weight cut off 500 kD, membrane) The whole amount was filtered using an area of 0.1 m 2 ). The amount of liquid (concentrated liquid) that did not permeate the filter membrane was 363 g, its conductivity was 2.00 mS / cm, and the solid content concentration was 33%.
Separately, an aqueous sodium hydrogen carbonate solution was prepared so that the electrical conductivity was 2.20 mS / cm, and 37 g was added to the liquid that did not permeate the filter membrane (concentrated liquid) as an amount corresponding to the membrane permeate and mixed. However, no thickening was observed.
The filtration process was repeated to perform a total of 25 passes. The removal rate of the water-insoluble polymer in each pass is as follows: after 1 pass: removal rate 0%, after 3 passes: removal rate 4%, after 6 passes: removal rate 7%, after 9 passes: removal rate 10%, 15 passes After: removal rate 15%, after 25 passes: removal rate 24%.
The viscosity of the aqueous pigment dispersion obtained by adjusting the aqueous pigment dispersion having a solid content concentration of 33% obtained after 25 membrane treatments to 30% using ion-exchanged water is 7.28 mPa · s, and its conductivity is 2. The conductivity was 11 mS / cm, and the conductivity was 97.7% before the film treatment.
（３）水系インクの調製
上記（２）で得られた水系顔料分散体に、以下の混合溶液を添加し顔料分換算重量が１０．０部となるように調製した。
水溶性有機溶媒である１，２−ヘキサンジオール（東京化成工業株式会社製、溶解度パラメーター１３．１５）２．０部、２−ピロリドン（和光純薬株式会社製、溶解度パラメーター１３．６６）２．０部、グリセリン（花王株式会社製、溶解度パラメーター１９．４４）２．０部、トリエチレングリコールモノブチルエーテル（商品名：ブチルトリグリコール、日本乳化剤株式会社製、溶解度パラメーター１０．２１）１０．０部、ノニオン界面活性剤であるサーフィノール４６５（日信化学工業株式会社製）０．５部、オルフィンＥ１０１０（日信化学工業株式会社製）０．５部、防腐剤であるプロキセルＸＬ２（アビシア株式会社製、）０．３部、及びイオン交換水をマグネチックスターラーで撹拌しながら混合し、更に室温で１５分間攪拌して、混合溶液を得た。ここで混合溶液と前記水系顔料分散体を加えた全量が１００部となるように、イオン交換水を加えて調整した。
次に、前記水系顔料分散体をマグネチックスターラーで撹拌しながら、前記混合溶液を添加し、５μｍのフィルター（酢酸セルロース膜、ザルトリウス社製）で濾過し、水系インクを得た。得られたインクの保存安定性は１０８％であった。
(3) Preparation of water-based ink To the water-based pigment dispersion obtained in (2) above, the following mixed solution was added to prepare a pigment equivalent weight of 10.0 parts.
1. 1,2-hexanediol which is a water-soluble organic solvent (Tokyo Chemical Industry Co., Ltd., solubility parameter 13.15) 2.0 parts, 2-pyrrolidone (Wako Pure Chemical Industries, Ltd. solubility parameter 13.66) 0 parts, 2.0 parts of glycerin (manufactured by Kao Corporation, solubility parameter 19.44), 10.0 parts of triethylene glycol monobutyl ether (trade name: butyltriglycol, manufactured by Nippon Emulsifier Co., Ltd., solubility parameter 10.21) , Surfionol 465 which is a nonionic surfactant (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 part, Olphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) 0.5 part, Proxel XL2 which is a preservative (Avicia Co., Ltd.) 0.3 parts) and ion-exchanged water are mixed with stirring with a magnetic stirrer, and further 15 minutes at room temperature. And stirred to obtain a mixed solution. Here, ion-exchanged water was added and adjusted so that the total amount of the mixed solution and the aqueous pigment dispersion was 100 parts.
Next, while stirring the aqueous pigment dispersion with a magnetic stirrer, the mixed solution was added and filtered through a 5 μm filter (cellulose acetate membrane, manufactured by Sartorius) to obtain an aqueous ink. The storage stability of the obtained ink was 108%.
比較例１
実施例１（１）で得られた顔料を含有する架橋ポリマー粒子の水分散体（固形分濃度３０％、導電率２．１６ｍＳ／ｃｍ）を用いて、実施例１（３）と同様にしてインクを調製した。その結果、７０℃、１週間の保存試験結果でインク粘度は上昇し、インクの保存安定性は１５０％であった。
比較例２
実施例１（１）で得られた顔料を含有する架橋ポリマー粒子の水分散体（固形分濃度３０％、導電率２．１６ｍＳ／ｃｍ）を用いて、実施例１（２）の炭酸水素ナトリウム水溶液に変えて、イオン交換水を用いて膜処理を行った。９パスまで行った時点で分散体が増粘し、それ以降の処理の継続が不可能であった。各パス回数における水不溶性ポリマーの除去率は、３パス後：除去率４％、６パス後：除去率７％、９パス後：除去率１０％であった。
９パス処理時にろ過膜を透過しなかった固形分濃度３３％の分散体を固形分濃度３０％に調整した分散体の粘度は２４ｍＰａ・ｓ、導電率は１．２８ｍＳ／ｃｍであった。
比較例３
実施例１（１）で得られた顔料を含有する架橋ポリマー粒子の水分散体（固形分濃度３０％、導電率２．１６ｍＳ／ｃｍ）を用いて、実施例１（２）の炭酸水素ナトリウム水溶液に変えて、導電率２．５０ｍＳ／ｃｍの炭酸水素ナトリウムを調製し、１パス後に、膜透過液と同量添加した。その際の水分散体の固形分濃度は３０％、導電率は２．３５ｍＳ／ｃｍ、粘度は６．９８ｍＰａ・ｓで減粘する傾向が認められたので、さらに同様のろ過操作を繰り返した。５パス時には、分散体の粘度が上昇し、膜処理の操作が実質的にできないところまでろ過速度が低下した。
５パス後のろ膜を透過しなかった固形分濃度３３％の分散体を固形分濃度３０％に調整した分散体の粘度は、２０ｍＰａ・ｓ、導電率は２．９８ｍＳ／ｃｍであった。
Comparative Example 1
In the same manner as in Example 1 (3), using an aqueous dispersion of the crosslinked polymer particles containing the pigment obtained in Example 1 (1) (solid content concentration 30%, conductivity 2.16 mS / cm). An ink was prepared. As a result, the ink viscosity increased as a result of a storage test at 70 ° C. for one week, and the storage stability of the ink was 150%.
Comparative Example 2
Using the aqueous dispersion of the crosslinked polymer particles containing the pigment obtained in Example 1 (1) (solid content concentration 30%, conductivity 2.16 mS / cm), sodium hydrogen carbonate of Example 1 (2) Instead of the aqueous solution, membrane treatment was performed using ion-exchanged water. When up to 9 passes, the dispersion thickened and it was not possible to continue processing thereafter. The removal rate of the water-insoluble polymer in each pass was as follows: 3 pass: removal rate 4%, 6 pass: removal rate 7%, 9 pass: removal rate 10%.
The viscosity of a dispersion prepared by adjusting a dispersion having a solid content concentration of 33% that did not permeate the filtration membrane during 9-pass treatment to a solid content concentration of 30% was 24 mPa · s, and the conductivity was 1.28 mS / cm.
Comparative Example 3
Using the aqueous dispersion of the crosslinked polymer particles containing the pigment obtained in Example 1 (1) (solid content concentration 30%, conductivity 2.16 mS / cm), sodium hydrogen carbonate of Example 1 (2) Instead of the aqueous solution, sodium hydrogen carbonate having a conductivity of 2.50 mS / cm was prepared, and after one pass, the same amount as the membrane permeate was added. At that time, the solid content concentration of the aqueous dispersion was 30%, the conductivity was 2.35 mS / cm, and the viscosity was 6.98 mPa · s. During the 5th pass, the viscosity of the dispersion increased, and the filtration rate decreased to the point where membrane treatment could not be performed.
The viscosity of the dispersion prepared by adjusting the dispersion having a solid content concentration of 33% that did not permeate the filter membrane after 5 passes to a solid content concentration of 30% was 20 mPa · s, and the conductivity was 2.98 mS / cm.
表２に示したとおり、水分散体の導電率を〔膜処理前の水分散体の導電率±２５％〕の範囲内に保持しつつ膜処理し、膜処理前における顔料に吸着していない水不溶性ポリマー量の５重量％以上を除去すると、生産性よく、保存安定性の優れた水系顔料分散体を製造することができる。 As shown in Table 2, the membrane was treated while maintaining the conductivity of the aqueous dispersion within the range of [conductivity of aqueous dispersion before membrane treatment ± 25%], and was not adsorbed by the pigment before membrane treatment. When 5% by weight or more of the water-insoluble polymer amount is removed, an aqueous pigment dispersion having good productivity and excellent storage stability can be produced.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009200712A JP5448650B2 (en) | 2009-08-31 | 2009-08-31 | Method for producing aqueous pigment dispersion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009200712A JP5448650B2 (en) | 2009-08-31 | 2009-08-31 | Method for producing aqueous pigment dispersion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011052070A JP2011052070A (en) | 2011-03-17 |
| JP5448650B2 true JP5448650B2 (en) | 2014-03-19 |
Family
ID=43941404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009200712A Active JP5448650B2 (en) | 2009-08-31 | 2009-08-31 | Method for producing aqueous pigment dispersion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5448650B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6107244B2 (en) * | 2013-03-08 | 2017-04-05 | コニカミノルタ株式会社 | Fluorescent dye labeling resin particles, production method thereof, and tissue immunostaining kit containing the particles |
| JP6519766B2 (en) * | 2013-11-22 | 2019-05-29 | 花王株式会社 | Pigment water dispersion for inkjet recording |
| EP3072935B1 (en) * | 2013-11-22 | 2020-10-21 | Kao Corporation | Pigment aqueous dispersion for inkjet recording |
| JP6412686B2 (en) * | 2013-11-22 | 2018-10-24 | 花王株式会社 | Method for producing pigment aqueous dispersion for inkjet recording |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11152424A (en) * | 1997-11-25 | 1999-06-08 | Dainippon Ink & Chem Inc | Production of aqueous pigment dispersion and aqueous colored liquid |
| JP2001207104A (en) * | 2000-01-24 | 2001-07-31 | Dainippon Ink & Chem Inc | Water-based pigment dispersion and water-based recording liquid |
| JP2002327144A (en) * | 2000-06-28 | 2002-11-15 | Seiko Epson Corp | Method of producing pigment dispersion, pigment dispersion and ink jet recording ink using the same |
| JP2003268269A (en) * | 2002-03-14 | 2003-09-25 | Ricoh Co Ltd | Water-base ink and inkjet recording apparatus |
| JP2003342493A (en) * | 2002-05-27 | 2003-12-03 | Konica Minolta Holdings Inc | Method of purifying organic compound |
| JP2005120136A (en) * | 2003-10-14 | 2005-05-12 | Seiko Epson Corp | Microencapsulated pigment and method for producing the same, aqueous dispersion and ink for ink-jet recording |
| JP4071244B2 (en) * | 2005-02-24 | 2008-04-02 | 東芝テック株式会社 | Method for producing powder dispersion, method for producing pigment dispersion, and method for producing inkjet ink |
| JP2008239961A (en) * | 2007-02-26 | 2008-10-09 | Mitsubishi Chemicals Corp | Aqueous pigment dispersion, process for producing the same, and recording liquid comprising the same |
| JP5227534B2 (en) * | 2007-04-16 | 2013-07-03 | 花王株式会社 | Method for producing aqueous pigment dispersion |
-
2009
- 2009-08-31 JP JP2009200712A patent/JP5448650B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011052070A (en) | 2011-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI424029B (en) | Process, composition and ink | |
| JP5448650B2 (en) | Method for producing aqueous pigment dispersion | |
| JP2008031194A (en) | Self-dispersed colored particulates, aqueous dispersion containing the same, and ink for inkjet recording or ink for color filter | |
| JP5600425B2 (en) | Method for producing aqueous dispersion for ink jet recording | |
| JP4302940B2 (en) | Ink set for inkjet recording | |
| JP5599998B2 (en) | Method for producing aqueous dispersion for ink jet recording | |
| JP2006176759A (en) | Aqueous pigment dispersion and inkjet ink composition | |
| JP2007231074A (en) | Aqueous pigment dispersion and ink composition using the same | |
| JP2005002186A (en) | Inkjet ink composition | |
| JP2011127064A (en) | Water-based ink for inkjet recording | |
| JP2006131900A (en) | Polymeric emulsion for inkjet ink | |
| WO2000004102A1 (en) | Ink jet recording ink, ink jet recording method and recordings | |
| JP5588322B2 (en) | Method for producing water-based ink for inkjet recording | |
| JPH11166131A (en) | Carbon black dispersed liquid, manufacture thereof and ink composition | |
| JP5368874B2 (en) | Method for producing aqueous dispersion for ink jet recording | |
| JP2007169359A (en) | Aqueous pigment dispersion and ink composition using the same | |
| JP5010362B2 (en) | Water-based ink for inkjet recording | |
| JP2006206626A (en) | Water-based pigment dispersion and ink composition using the same | |
| WO2019239957A1 (en) | Ink and printed matter | |
| JP2007077340A (en) | Aqueous pigment dispersion and ink composition using the same | |
| JP6294658B2 (en) | Method for producing pigment aqueous dispersion for inkjet recording | |
| JP5544094B2 (en) | Water-based ink for inkjet recording | |
| JP2008144098A (en) | Aqueous pigment dispersion and ink composition using the same | |
| JP6644995B2 (en) | Method for producing aqueous ink for inkjet recording | |
| JP2017114980A (en) | Method for producing pigment aqueous dispersion for inkjet recording |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120612 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130905 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130910 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20131025 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20131203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20131224 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 5448650 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |