JP4802510B2 - Disazo pigment composition and method for producing the same - Google Patents
Disazo pigment composition and method for producing the same Download PDFInfo
- Publication number
- JP4802510B2 JP4802510B2 JP2005048770A JP2005048770A JP4802510B2 JP 4802510 B2 JP4802510 B2 JP 4802510B2 JP 2005048770 A JP2005048770 A JP 2005048770A JP 2005048770 A JP2005048770 A JP 2005048770A JP 4802510 B2 JP4802510 B2 JP 4802510B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- fatty acid
- acid ester
- sorbitan fatty
- pigment
- 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.)
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- 239000000049 pigment Substances 0.000 title claims description 166
- 239000000203 mixture Substances 0.000 title claims description 70
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 86
- -1 sorbitan fatty acid ester Chemical class 0.000 claims description 77
- 239000000976 ink Substances 0.000 claims description 70
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 63
- 239000000194 fatty acid Substances 0.000 claims description 63
- 229930195729 fatty acid Natural products 0.000 claims description 63
- 239000003973 paint Substances 0.000 claims description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 27
- 238000005859 coupling reaction Methods 0.000 claims description 25
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 15
- HUWXDEQWWKGHRV-UHFFFAOYSA-N 3,3'-Dichlorobenzidine Chemical compound C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HUWXDEQWWKGHRV-UHFFFAOYSA-N 0.000 claims description 13
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000008878 coupling Effects 0.000 claims description 7
- 238000010168 coupling process Methods 0.000 claims description 7
- 238000004040 coloring Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 14
- 238000007646 gravure printing Methods 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 239000007900 aqueous suspension Substances 0.000 description 12
- 239000002736 nonionic surfactant Substances 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 9
- 239000002609 medium Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 238000007639 printing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000001052 yellow pigment Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 4
- 239000008135 aqueous vehicle Substances 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006193 diazotization reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229940035044 sorbitan monolaurate Drugs 0.000 description 3
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 2
- LPDSNGAFAJYVKH-UHFFFAOYSA-N 4-(4-aminophenyl)-2,3-dichloroaniline Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C(Cl)=C1Cl LPDSNGAFAJYVKH-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
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- 229920001213 Polysorbate 20 Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical group CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 244000144992 flock Species 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 2
- 229920000053 polysorbate 80 Polymers 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 239000001593 sorbitan monooleate Substances 0.000 description 2
- 235000011069 sorbitan monooleate Nutrition 0.000 description 2
- 229940035049 sorbitan monooleate Drugs 0.000 description 2
- 239000001587 sorbitan monostearate Substances 0.000 description 2
- 235000011076 sorbitan monostearate Nutrition 0.000 description 2
- 229940035048 sorbitan monostearate Drugs 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- BXAONUZFBUNTQR-UHFFFAOYSA-N 4-(4-amino-3-chlorophenyl)-2-chloroaniline;hydron;dichloride Chemical compound Cl.Cl.C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 BXAONUZFBUNTQR-UHFFFAOYSA-N 0.000 description 1
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 0 CC(C(C(Nc1ccccc1C)=O)=NNc(c(Cl)c1)ccc1-c(cc1)cc(Cl)c1NN=C(C(*)=O)C(Nc1ccccc1C)=O)=O Chemical compound CC(C(C(Nc1ccccc1C)=O)=NNc(c(Cl)c1)ccc1-c(cc1)cc(Cl)c1NN=C(C(*)=O)C(Nc1ccccc1C)=O)=O 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001219 Polysorbate 40 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- PZQBWGFCGIRLBB-NJYHNNHUSA-N [(2r)-2-[(2s,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1O PZQBWGFCGIRLBB-NJYHNNHUSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 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
- 239000012153 distilled water Substances 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paints Or Removers (AREA)
Description
本発明は、水性インキや水性塗料へ加えた時に発泡しにくく、分散性が良好でありかつ高着色力の着色物が得られる、C.I.ピグメントイエロー14を主成分として含有するジスアゾ顔料組成物及びその製造方法に関する。 In the present invention, when added to water-based ink or water-based paint, it is difficult to foam, a dispersibility is good, and a colored product having high coloring power is obtained. I. The present invention relates to a disazo pigment composition containing Pigment Yellow 14 as a main component and a method for producing the same.
C.I.ピグメントイエロー14は、類似構造の不溶性ジスアゾ顔料であるC.I.ピグメントイエロー12やC.I.ピグメントイエロー13と異なる緑味の黄色を呈することが知られている。そして、C.I.ピグメントイエロー12に比べて耐溶剤性や耐光性に優れるため、軽包装グラビア印刷インキ等の調製により多く用いられている。 C. I. Pigment Yellow 14 is an insoluble disazo pigment having a similar structure. I. Pigment yellow 12 and C.I. I. It is known to exhibit a greenish yellow color different from Pigment Yellow 13. And C.I. I. Since it is excellent in solvent resistance and light resistance as compared with CI Pigment Yellow 12, it is often used for the preparation of light packaging gravure printing ink and the like.
印刷インキや塗料は、油性と水性の二種類があるが、最近では大気汚染や作業環境汚染の問題により、いずれも積極的に水性化がすすめられている。C.I.ピグメントイエロー14に代表される不溶性ジスアゾ顔料は疎水性が極めて高いため、それを水性媒体に安定的に分散させるためには、不溶性ジスアゾ顔料表面の親水性を今まで以上に向上させる必要がある。 There are two types of printing inks and paints, oily and water-based. Recently, water-based printing inks and paints are actively promoted due to problems of air pollution and work environment pollution. C. I. Since the insoluble disazo pigment represented by Pigment Yellow 14 has extremely high hydrophobicity, in order to stably disperse it in an aqueous medium, it is necessary to improve the hydrophilicity of the surface of the insoluble disazo pigment more than ever.
顔料表面を親水性にして水性媒体中における分散性を向上させる方法としては、ポリオキシエチレンノニルフェノールエーテルの様なHLB13を越える様なノニオン性界面活性剤で顔料の表面を被覆することが従来行われていた。しかしながら、この方法での顔料表面の親水性化は、用いられる界面活性剤が逆に水性インキの発泡の要因となってしまうためにその使用量が限定されてしまい充分に表面を親水性にすることは困難であった。この様な界面活性剤のみでは十分に顔料表面を親水性にすることは不可能であった。 As a method for improving the dispersibility in an aqueous medium by making the pigment surface hydrophilic, the pigment surface is conventionally coated with a nonionic surfactant that exceeds HLB13, such as polyoxyethylene nonylphenol ether. It was. However, the hydrophilicity of the pigment surface by this method is constrained by the fact that the surfactant used causes foaming of the water-based ink, so that the amount used is limited and the surface is made sufficiently hydrophilic. It was difficult. It was impossible to make the pigment surface sufficiently hydrophilic with such a surfactant alone.
これに対して特許文献1には、ソルビタンジステアレートやソルビタントリオレエートの様なHLB2〜5のノニオン性界面活性剤を主体として、これにHLB13を越えるノニオン性界面活性剤を併用して顔料の表面を被覆することが記載されている。
しかしながら、インキ化分散時の粘度が高く、高顔料分での分散が出来ず、顔料分を下げて分散してもインキ展色物の光沢、着色力に劣る欠点があった。
On the other hand, in Patent Document 1, a nonionic surfactant having HLB 2 to 5 such as sorbitan distearate or sorbitan trioleate is mainly used, and a nonionic surfactant exceeding HLB13 is used in combination with this. The coating of the surface is described.
However, the viscosity at the time of ink dispersion is high, the dispersion with a high pigment content cannot be performed, and even when the pigment content is lowered and dispersed, there is a defect that the gloss and coloring power of the ink extended product are inferior.
特許文献2には、エチレンジアミンのエチレンオキサイド−プロピレンオキサイド付加物からなるノニオン性界面活性剤を併用して顔料の表面を被覆することが記載されている。
しかしながら、インキ化分散時の粘度が高く、高顔料分での分散が出来ず、顔料分を下げて分散してもインキ展色物の光沢、着色力に劣る欠点があった。
Patent Document 2 describes that the surface of a pigment is coated with a nonionic surfactant composed of an ethylene oxide-propylene oxide adduct of ethylenediamine.
However, the viscosity at the time of ink dispersion is high, the dispersion with a high pigment content cannot be performed, and even when the pigment content is lowered and dispersed, there is a defect that the gloss and coloring power of the ink extended product are inferior.
特許文献3には、水性媒体中で有機溶剤の不存在下に一段階でカップリング反応を行って不溶性ジスアゾ顔料を製造する際に、遅くとも顔料を単離する直前までに水溶液状態で濁り点を持つノニオン性界面活性剤を添加することで、顔料の表面を被覆することが記載されている。
特許文献3に記載されている濁り点を持つノニオン性界面活性剤は、プロピレンオキサイド−エチレンオキサイドブロック共重合体等であるが、これらで表面被覆した顔料は、インキ化の光沢、透明性、着色力のいずれも未処理のC.I.ピグメントイエロー14と何ら変わらない品質であり、水性媒体に安定的に分散させることは困難であった。
In Patent Document 3, when an insoluble disazo pigment is produced by carrying out a coupling reaction in an aqueous medium in the absence of an organic solvent in one step, a turbid point in an aqueous solution state is required at the latest just before the pigment is isolated. It is described that the surface of a pigment is coated by adding a nonionic surfactant.
The nonionic surfactant having a turbidity point described in Patent Document 3 is a propylene oxide-ethylene oxide block copolymer or the like. However, the pigment whose surface is coated with these has gloss, transparency, and coloring of ink. None of the forces are untreated C.I. I. It was of the same quality as Pigment Yellow 14, and it was difficult to stably disperse it in an aqueous medium.
特許文献4には、不溶性ジスアゾ顔料の製造工程において、カップラースラリー中又はカップリング終了後の顔料スラリー中或いは乾燥顔料中に、不飽和多価脂肪酸とロジンとのディールスアルダー縮合物を加えること、さらに必要に応じてノニオン性界面活性剤を添加することで、顔料の表面を被覆することが記載されている。
しかしながら、特許文献4に記載されているノニオン性界面活性剤は、インキ化分散時の粘度が高く、高顔料分での分散が出来ず、顔料分を下げて分散してもインキ展色物の光沢、着色力に劣るという欠点があった。
In Patent Document 4, in the production process of an insoluble disazo pigment, a Diels-Alder condensate of unsaturated polyvalent fatty acid and rosin is added to the coupler slurry, the pigment slurry after the coupling, or the dried pigment, and It is described that the surface of the pigment is coated by adding a nonionic surfactant as required.
However, the nonionic surfactant described in Patent Document 4 has a high viscosity at the time of ink dispersion, and cannot be dispersed with a high pigment content. There was a disadvantage that it was inferior in gloss and coloring power.
不溶性アゾ顔料は水系で合成することが多く顔料スラリー中ではフロック状態になっておりこのフロックの状態を解膠させるために、ノニオン性界面活性剤で顔料の表面を被覆すると、一方で、顔料濾過単離後の乾燥・粉末化で、水性インキや水性塗料に用いた時に、それらの品質が表面被覆する前の状態の顔料よりも悪化してしまうという欠点がある。 Insoluble azo pigments are often synthesized in an aqueous system and are in a floc state in the pigment slurry. In order to remove the floc state, the surface of the pigment is coated with a nonionic surfactant. When used in water-based inks or water-based paints after drying and powdering after isolation, there is a drawback that their quality is worse than that of the pigment in a state before surface coating.
従って、水性インキや水性塗料の調製に適した、発泡しにくく被着色媒体への分散性が良好でありかつ高着色力の着色物が得られるC.I.ピグメントイエロー14を主成分として含有するジスアゾ顔料組成物が望まれている。
本発明は、水性インキや水性塗料の調製に適し、被着色媒体への分散性が良好でありかつ高着色力の着色物が得られるC.I.ピグメントイエロー14を主成分として含有するジスアゾ顔料組成物を提供することを目的とする。 The present invention is suitable for the preparation of water-based inks and water-based paints, and has a good dispersibility in a medium to be colored and can give a colored product having high coloring power. I. It is an object to provide a disazo pigment composition containing Pigment Yellow 14 as a main component.
本発明者等は、C.I.ピグメント イエロー14を主成分とする系において、被着色媒体への分散性が良好でありかつ高着色力の着色物が得られる様に鋭意検討した結果、顔料分子に対する吸着点となる親水基として水酸基を比較的多く含有する特定化学構造のノニオン性界面活性剤をC.I.ピグメント イエロー14に含有させ、かつ顔料に含まれる酸成分を充分に中和して抽出液のpH値がアルカリ性となるまでにすることで上記した課題が解決されること、またこの様な顔料組成物は、顔料製造後に行われる濾過より以前に特定化学構造のノニオン性界面活性剤を系内に含有させておき、顔料スラリーの加熱熟成をアルカリ性にて行うことで、容易に製造出来ることを見い出し、本発明を完成するに至った。 The inventors have described C.I. I. As a result of diligent research to obtain a colored product having good dispersibility in a medium to be colored and high coloring power in a system mainly containing CI Pigment Yellow 14, a hydroxyl group as a hydrophilic group serving as an adsorption point for pigment molecules is obtained. A nonionic surfactant having a specific chemical structure and containing a relatively large amount of C.I. I. Pigment Yellow 14 and the above-mentioned problems can be solved by sufficiently neutralizing the acid component contained in the pigment until the pH value of the extract becomes alkaline, and such a pigment composition. It is found that the product can be easily manufactured by adding a nonionic surfactant having a specific chemical structure in the system prior to the filtration performed after the pigment is manufactured, and performing the heat aging of the pigment slurry in an alkaline manner. The present invention has been completed.
即ち本発明は、質量換算で、C.I.ピグメントイエロー14の99〜95%と、水酸基を2〜5個含有する、ソルビタン脂肪酸エステル又はポリオキシエチレンソルビタン脂肪酸エステルの1〜5%を含有し、日本工業規格JIS K 5101−17−1に定めるpH値が8〜11である、水性インキ又は水性塗料用ジスアゾ顔料組成物を提供する。 That is, the present invention is C.I. I. It contains 99 to 95% of Pigment Yellow 14 and 1 to 5% of sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups, and is defined in Japanese Industrial Standard JIS K 5101-17-1. Provided is a disazo pigment composition for water-based ink or water-based paint having a pH value of 8-11.
また本発明は、質量換算で、C.I.ピグメントイエロー14の95〜99%と、水酸基を2〜5個含有する、ソルビタン脂肪酸エステル又はポリオキシエチレンソルビタン脂肪酸エステルの1〜5%とを含有する水性インキ又は水性塗料用ジスアゾ顔料組成物の製造方法であり、3,3´−ジクロロベンジジンのテトラゾニウム塩とアセト酢酸−o−トルイダイドとをカップリングさせてC.I.ピグメントイエロー14とし、加熱熟成し濾過洗浄する水性インキ又は水性塗料用ジスアゾ顔料組成物の製造方法において、濾過以前の任意の段階において、水酸基を2〜5個含有する、ソルビタン脂肪酸エステル又はポリオキシエチレンソルビタン脂肪酸エステルを含有させると共に、加熱熟成をアルカリ性にて行うことを特徴とする水性インキ又は水性塗料用ジスアゾ顔料組成物の製造方法を提供する。 Further, the present invention is C.I. I. Manufacture of a disazo pigment composition for aqueous ink or aqueous paint containing 95 to 99% of Pigment Yellow 14 and 1 to 5% of sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups A method comprising coupling a tetrazonium salt of 3,3′-dichlorobenzidine and acetoacetic acid-o-toluidide to form C.I. I. Sorbitan fatty acid ester or polyoxyethylene containing 2 to 5 hydroxyl groups at any stage prior to filtration in a method for producing a disazo pigment composition for water-based inks or water-based paints that is Pigment Yellow 14, heat-aged and filtered and washed Provided is a method for producing a disazo pigment composition for water-based inks or water-based paints, which contains a sorbitan fatty acid ester and is heated and aged in an alkaline manner.
本発明のジスアゾ顔料組成物は、C.I.ピグメントイエロー14と特定化学構造のノニオン性界面活性剤とを含有し、従来より高いpH値を有するので、水性インキ又は水性塗料に適用した際、発泡しにくく被着色媒体への分散性が良好でありかつ高着色力の着色物が得られるという格別顕著な効果を奏する。
また本発明のジスアゾ顔料組成物の製造方法は、水性インキ又は水性塗料に適用した際、発泡しにくく被着色媒体への分散性が良好でありかつ高着色力の着色物が得られるジスアゾ顔料組成物を、より簡便に製造できるという格別顕著な効果を奏する。
The disazo pigment composition of the present invention comprises C.I. I. It contains CI Pigment Yellow 14 and a nonionic surfactant having a specific chemical structure, and has a higher pH value than before. Therefore, when applied to water-based ink or water-based paint, it is difficult to foam and has good dispersibility in the medium to be colored. There is a particularly remarkable effect that a colored product having high coloring power can be obtained.
The method for producing the disazo pigment composition of the present invention is a disazo pigment composition that, when applied to water-based inks or water-based paints, is difficult to foam and has a good dispersibility in a medium to be colored and provides a colored product with high coloring power. There is an especially remarkable effect that the product can be manufactured more easily.
本発明のジスアゾ顔料組成物は、質量換算でC.I.ピグメントイエロー14と、水酸基を2〜5個含有する、ソルビタン脂肪酸エステル又はポリオキシエチレンソルビタン脂肪酸エステルとの合計を100%としたとき、C.I.ピグメントイエロー14の99〜95%と、水酸基を2〜5個含有する、ソルビタン脂肪酸エステル又はポリオキシエチレンソルビタン脂肪酸エステルの1〜5%とを含有する。 The disazo pigment composition of the present invention has C.I. I. When the total of CI Pigment Yellow 14 and a sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups is 100%, C.I. I. It contains 99 to 95% of CI Pigment Yellow 14 and 1 to 5% of sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups.
C.I.ピグメントイエロー14は、公知慣用の不溶性ジスアゾ顔料であり、下記式にて表される物質からなる。 C. I. Pigment Yellow 14 is a known and commonly used insoluble disazo pigment, and is made of a substance represented by the following formula.
また本発明のジスアゾ顔料組成物は、水酸基を2〜5個含有する、ソルビタン脂肪酸エステル又はポリオキシエチレンソルビタン脂肪酸エステルを含有する。これらは、C.I.ピグメントイエロー14に吸着し、凝集体(フロック)となったC.I.ピグメントイエロー14をより弱い力で解れ易くさせるために用いられる。ソルビタン脂肪酸エステルとしては、水酸基を含有しないものもあるが、本発明の効果を得るためには顔料分子への吸着点となる有力な親水基である水酸基をより多く含有していることが好ましいため、水酸基を2〜5個含有するソルビタン脂肪酸エステルを選択して用いる。水酸基を2〜5個含有するソルビタン脂肪酸エステルとしては、例えば、下記式にて表される物質が挙げられる。式中、Rは炭素原子数10〜24の分岐を有していても良い、アルキル基又はアルケニル基である。 The disazo pigment composition of the present invention contains a sorbitan fatty acid ester or polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups. These are C.I. I. Pigment Yellow 14 adsorbed to form aggregates (floc). I. It is used to make Pigment Yellow 14 easier to unravel with a weaker force. Some sorbitan fatty acid esters do not contain hydroxyl groups, but in order to obtain the effects of the present invention, it is preferable to contain more hydroxyl groups that are effective hydrophilic groups that serve as adsorption points to pigment molecules. A sorbitan fatty acid ester containing 2 to 5 hydroxyl groups is selected and used. Examples of the sorbitan fatty acid ester containing 2 to 5 hydroxyl groups include substances represented by the following formula. In the formula, R is an alkyl group or an alkenyl group which may have a branch having 10 to 24 carbon atoms.
水酸基を2〜5個含有するソルビタン脂肪酸エステルとしては、例えば、ソルビタンモノステアレート(R=C17H35)、ソルビタンモノオレエート(R=C17H33)、ソルビタンモノパルミテート(R=C15H31)等が挙げられる。 Examples of the sorbitan fatty acid ester containing 2 to 5 hydroxyl groups include sorbitan monostearate (R = C17H35), sorbitan monooleate (R = C17H33), sorbitan monopalmitate (R = C15H31), and the like.
ポリオキシエチレンソルビタン脂肪酸エステルとしても、水酸基を含有しないものもあるが、上記ソルビタン脂肪酸エステルと同様の理由で、水酸基を2〜5個含有するポリオキシエチレンソルビタン脂肪酸エステルを選択して用いる。水酸基を2〜5個含有するポリオキシエチレンソルビタン脂肪酸エステルとしては、下記式にて表される物質が挙げられる。式中、Rは上記と同義であり、m、l及びnは、いずれもポリオキシエチレンの繰り返し単位数であり、それらの合計m+l+n=15〜30である。 Although some polyoxyethylene sorbitan fatty acid esters do not contain a hydroxyl group, a polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups is selected and used for the same reason as the sorbitan fatty acid ester. Examples of the polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups include substances represented by the following formula. In the formula, R is as defined above, and m, l, and n are all the number of repeating units of polyoxyethylene, and the total thereof is m + 1 + n = 15-30.
水酸基を2〜5個含有するポリオキシエチレンソルビタン脂肪酸エステルとしては、例えば、ポリオキシエチレン(6)ソルビタンモノラウレート(R=C11H23)、ポリオキシエチレン(20)ソルビタンモノラウレート(R=C11H23)、ポリオキシエチレン(20)ソルビタンモノパルミテート(R=C15H31)、ポリオキシエチレン(6)ソルビタンモノステアレート(R=C17H35)、ポリオキシエチレン(20)ソルビタンモノオレエート(R=C17H33)等が挙げられる。ここで( )内の数字は、ポリオキシエチレンの繰り返し単位数の総和m+l+nである。 Examples of the polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups include polyoxyethylene (6) sorbitan monolaurate (R = C11H23) and polyoxyethylene (20) sorbitan monolaurate (R = C11H23). Polyoxyethylene (20) sorbitan monopalmitate (R = C15H31), polyoxyethylene (6) sorbitan monostearate (R = C17H35), polyoxyethylene (20) sorbitan monooleate (R = C17H33), etc. Can be mentioned. Here, the numbers in parentheses are the sum m + l + n of the number of repeating units of polyoxyethylene.
これら水酸基を2〜5個含有するソルビタン脂肪酸エステルと、水酸基を2〜5個含有するポリオキシエチレンソルビタン脂肪酸エステルとは、それぞれを単独で用いても良いし、両者を併用しても良い。以下、水酸基を2〜5個含有するソルビタン脂肪酸エステルと、水酸基を2〜5個含有するポリオキシエチレンソルビタン脂肪酸エステルをあわせて、脂肪酸エステルと略記する。 These sorbitan fatty acid esters containing 2 to 5 hydroxyl groups and polyoxyethylene sorbitan fatty acid esters containing 2 to 5 hydroxyl groups may be used alone or in combination. Hereinafter, a sorbitan fatty acid ester containing 2 to 5 hydroxyl groups and a polyoxyethylene sorbitan fatty acid ester containing 2 to 5 hydroxyl groups are collectively abbreviated as fatty acid esters.
この脂肪酸エステルは、どの様なHLB値を持つものであっても良いが、例えば、ポリオキシエチレン(6)ソルビタンモノラウレート、ポリオキシエチレン(20)ソルビタンモノラウレート、ポリオキシエチレン(20)ソルビタンモノオレエート等、HLB13〜17であるものが水性インキの調製に用いた場合には、印刷時の版かぶりが起こりにくく、塗膜物性としての耐ラミネート強度もより良好となるので好ましい。 The fatty acid ester may have any HLB value. For example, polyoxyethylene (6) sorbitan monolaurate, polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) When the HLB 13-17, such as sorbitan monooleate, is used for the preparation of a water-based ink, it is preferable because plate fogging during printing hardly occurs and the laminate strength resistance as a coating film property becomes better.
また本発明のジスアゾ顔料組成物は、日本工業規格JIS K 5101−17−1に定めるpH値が8〜11である。この規格は、顔料の水懸濁液を煮沸し、常温まで放冷した後にpH測定装置を用いて、水懸濁液のpHを測定するための試験方法を規定する。この試験方法により、乾燥顔料等に不可避的に含まれる恐れのある酸やアルカリの存在とその量を推定出来る。 The disazo pigment composition of the present invention has a pH value of 8 to 11 as defined in Japanese Industrial Standard JIS K 5101-17-1. This standard defines a test method for measuring the pH of an aqueous suspension using a pH measuring device after boiling the aqueous suspension of the pigment and allowing it to cool to room temperature. By this test method, it is possible to estimate the presence and amount of acid or alkali that may be inevitably contained in the dry pigment.
一般的に不溶性ジスアゾ顔料は、水系で合成するために顔料スラリー中ではフロック状態になっている上、カップリング反応が弱酸性にて行われるため、この酸がフロック内部に取り込まれ易い。フロック表面に存在する酸は、後の洗浄により除去することが出来るが、フロック内部に存在する酸まで充分に洗浄除去することは難しい。常態では溶出し難いフロック内部の酸であっても、湿熱条件等に曝された結果、外部に溶出して腐食等の原因となることがある。日本工業規格JIS K 5101−17−1では、顔料水懸濁液の煮沸を行うので、常態では溶出し難いフロック内部の酸をより的確に把握することが可能となる。本発明の顔料組成物では、フロック内部に存在する酸を中和するよりも多くのアルカリを、C.I.ピグメントイエロー14に含ませることにより、日本工業規格JIS K 5101−17−1に定めるpH値を8〜11となる様にした。 In general, insoluble disazo pigments are in a floc state in the pigment slurry for synthesis in an aqueous system, and the coupling reaction is carried out with weak acidity, so that this acid is easily taken into the floc. The acid present on the surface of the floc can be removed by subsequent cleaning, but it is difficult to sufficiently remove the acid existing inside the floc. Even if it is an acid inside the floc that is difficult to elute under normal conditions, the acid may elute outside as a result of exposure to wet heat conditions and the like, which may cause corrosion. In Japanese Industrial Standard JIS K 5101-17-1, since the pigment water suspension is boiled, it becomes possible to more accurately grasp the acid inside the floc that is difficult to elute under normal conditions. In the pigment composition of the present invention, more alkali than C.I. I. By including it in CI Pigment Yellow 14, the pH value defined in Japanese Industrial Standard JIS K 5101-17-1 was adjusted to 8-11.
このアルカリとしては、例えば、アンモニアや有機アミンを用いても良いが、水洗で、より容易に生成塩を除去出来る上、揮発により塩が酸に戻る心配もないことから、水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物を用いることが好ましい。 As this alkali, for example, ammonia or organic amine may be used, but the generated salt can be removed more easily by washing with water, and there is no fear of the salt returning to acid by volatilization. It is preferable to use an alkali metal hydroxide such as potassium.
本発明のジスアゾ顔料組成物には、水性インキや水性塗料の調製や皮膜特性等への妨げがない範囲において、必要であれば、そこにC.I.ピグメントイエロー14以外のその他の黄色ジスアゾ顔料、前記脂肪酸エステル以外の界面活性剤、ロジン類等を含有させても良い。 If necessary, the disazo pigment composition of the present invention may contain C.I. in a range that does not hinder the preparation of water-based inks and water-based paints and film properties. I. You may contain other yellow disazo pigments other than pigment yellow 14, surfactants other than the said fatty acid ester, rosins, and the like.
C.I.ピグメントイエロー14以外のその他の黄色有機顔料としては、例えば、C.I.ピグメントイエロー12、C.I.ピグメントイエロー13、C.I.ピグメントイエロー83等が挙げられる。これらは単独で又は二種以上を併用の上、本発明のジスアゾ顔料組成物に含有させることが出来る。 C. I. Examples of other yellow organic pigments other than CI Pigment Yellow 14 include C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. And CI Pigment Yellow 83. These can be contained alone or in combination of two or more in the disazo pigment composition of the present invention.
前記脂肪酸エステル以外の界面活性剤としては、例えば、ポリエチレングリコールモノアルキルエーテル、アルキルベンゼンスルホン酸塩、ポリオキシアルキレンアルキルエーテル燐酸塩等が挙げられる。これらは単独で又は二種以上を併用の上、本発明のジスアゾ顔料組成物に含有させることが出来る。 Examples of the surfactant other than the fatty acid ester include polyethylene glycol monoalkyl ether, alkylbenzene sulfonate, polyoxyalkylene alkyl ether phosphate, and the like. These can be contained alone or in combination of two or more in the disazo pigment composition of the present invention.
本発明のジスアゾ顔料組成物に含有させることが出来るロジン類としては、公知慣用のロジン類がいずれも挙げられるが、例えばアビエチン酸を主成分とするロジン、不均化ロジン、部分水素添加ロジン、完全水素添加ロジン、マレイン酸変性ロジン、フマル酸変性ロジン、重合ロジン、或いはこれらの水不溶性塩等が挙げられる。 Examples of the rosins that can be contained in the disazo pigment composition of the present invention include all known and commonly used rosins. For example, rosins mainly composed of abietic acid, disproportionated rosins, partially hydrogenated rosins, Examples include fully hydrogenated rosin, maleic acid-modified rosin, fumaric acid-modified rosin, polymerized rosin, and water-insoluble salts thereof.
本発明のジスアゾ顔料組成物は、日本工業規格JIS K 5101−17−1に定めるpH値8〜11のC.I.ピグメントイエロー14と前記脂肪酸エステルとを前記した質量割合となる様に適宜混合して調製しても良いが、3,3´−ジクロロベンジジンのテトラゾニウム塩とアセト酢酸−o−トルイダイドとをカップリングさせてC.I.ピグメントイエロー14とし、加熱熟成し濾過洗浄する水性インキ又は水性塗料用ジスアゾ顔料組成物の製造方法において、C.I.ピグメントイエロー14と前記脂肪酸エステルとが前記した質量割合となる様に、カップリング反応のための各原料の必要量を用い、濾過以前の任意の段階において、必要量の前記脂肪酸エステルを含有させると共に、加熱熟成をアルカリ性にて行うことによって、C.I.ピグメントイエロー14と前記脂肪酸エステルとの混合や被覆をより均一に行うことが可能である点で好ましい。 The disazo pigment composition of the present invention has a C.I. value of 8 to 11 defined in Japanese Industrial Standard JIS K 5101-17-1. I. Pigment Yellow 14 and the fatty acid ester may be prepared by appropriately mixing so as to have the above-described mass ratio, but a tetrazonium salt of 3,3′-dichlorobenzidine and acetoacetic acid-o-toluidide are coupled. C. I. In the method for producing a disazo pigment composition for water-based inks or water-based paints, which is Pigment Yellow 14 and heat-aged and filtered and washed, C.I. I. The necessary amount of each raw material for the coupling reaction is used so that the pigment yellow 14 and the fatty acid ester have the mass ratio described above, and the necessary amount of the fatty acid ester is contained in an arbitrary stage before filtration. By carrying out heat aging in an alkaline manner, C.I. I. It is preferable in that the pigment yellow 14 and the fatty acid ester can be mixed and coated more uniformly.
この製造方法は、常法に従ってジスアゾ顔料を製造し、加熱熟成し濾過洗浄する従来のC.I.ピグメントイエロー14の製造方法において、濾過以前の任意の段階において、生成するC.I.ピグメントイエロー14と含ませる前記脂肪酸エステルとの合計を質量換算で100%としたとき前記脂肪酸エステルが1〜5%となる様に含有させると共に、加熱熟成をアルカリ性にて行うものである。 In this production method, disazo pigments are produced in accordance with a conventional method, heated and aged, filtered and washed. I. In the production method of CI Pigment Yellow 14, the C.I. I. When the total of the pigment yellow 14 and the fatty acid ester to be contained is 100% in terms of mass, the fatty acid ester is contained in an amount of 1 to 5%, and heat aging is performed in an alkaline manner.
ここで前記脂肪酸エステルを含有させる濾過以前の任意の段階としては、例えば、カップリング反応前の原料の水懸濁液や水溶液、カップリング反応中の反応液、カップリング反応終了後加熱熟成前、加熱熟成中の水懸濁液、加熱熟成後の水懸濁液等が挙げられる。 Here, as an optional stage before the filtration containing the fatty acid ester, for example, an aqueous suspension or aqueous solution of the raw material before the coupling reaction, a reaction liquid during the coupling reaction, after the coupling reaction and before heat aging, Examples thereof include an aqueous suspension during heat aging and an aqueous suspension after heat aging.
次にC.I.ピグメントイエロー14を製造するためのカップリング反応について詳記する。このカップリング反応では、3,3´−ジクロロベンジジンのテトラゾニウム塩とアセト酢酸−o−トルイダイドとを反応させる。
3,3´−ジクロロベンジジンやアセト酢酸−o−トルイダイドとしては、公知慣用のものがいずれも使用出来るが、いずれも、極力、高純度品を用いることが好ましい。3,3´−ジクロロベンジジンは、塩酸塩として用いることも出来る。
Next, C.I. I. The coupling reaction for producing Pigment Yellow 14 will be described in detail. In this coupling reaction, a tetrazonium salt of 3,3′-dichlorobenzidine is reacted with acetoacetic acid-o-toluidide.
As 3,3′-dichlorobenzidine and acetoacetic acid-o-toluidide, any known and commonly used ones can be used, but it is preferable to use high-purity products as much as possible. 3,3′-Dichlorobenzidine can also be used as the hydrochloride.
ジアゾ成分は、3,3´−ジクロロベンジジンのテトラゾニウム塩のみであっても良いが、必要に応じて、ジアゾ成分全体の15モル%以内であれば、このジアゾ成分に、その他の芳香族アミンのテトラゾニウム塩やジアゾニウム塩を含ませることが出来る。 The diazo component may be only the tetrazonium salt of 3,3′-dichlorobenzidine, but if necessary, the diazo component may contain other aromatic amines within 15 mol% of the total diazo component. Tetrazonium salts and diazonium salts can be included.
カップラー成分も、アセト酢酸−o−トルイダイドのみであっても良いが、必要に応じて、カップラー成分の15モル%以内であれば、このカップラー成分に、アセト酢酸アニリド、アセト酢酸−m−キシリダイド等を含ませることが出来る。 The coupler component may also be only acetoacetic acid-o-toluidide, but if necessary, within 15 mol% of the coupler component, this coupler component may include acetoacetanilide, acetoacetate-m-xylide, etc. Can be included.
3,3´−ジクロロベンジジンのテトラゾニウム塩としては、常法に従って調製された水溶液又は水懸濁液を用いることが出来る。3,3´−ジクロロベンジジンと塩酸と亜硝酸塩とを低温で反応させることで、対応するテトラゾニウム塩を含むジアゾ成分の水溶液又は水懸濁液が得られる。アセト酢酸−o−トルイダイドとしては、常法に従って調製された水溶液を用いることが出来る。アセト酢酸−o−トルイダイドを水に分散させてアルカリ性として溶解させることで、カップラー成分の水溶液が得られる。 As the tetrazonium salt of 3,3′-dichlorobenzidine, an aqueous solution or a water suspension prepared according to a conventional method can be used. By reacting 3,3′-dichlorobenzidine, hydrochloric acid and nitrite at a low temperature, an aqueous solution or suspension of a diazo component containing the corresponding tetrazonium salt is obtained. As acetoacetic acid-o-toluidide, an aqueous solution prepared according to a conventional method can be used. An aqueous solution of a coupler component is obtained by dispersing acetoacetic acid-o-toluidide in water by dissolving it in water.
こうして得られたジアゾ成分とカップラー成分とを、前記脂肪酸エステルの存在下で、常法に従ってカップリングすることでC.I.ピグメントイエロー14の水懸濁液を調製することが出来る。この際、カップラー成分をジアゾ成分に加える様にしても良いし、カップラー成分にジアゾ成分を加える様にしても良いが、水に対してカップラー成分とジアゾ成分とを加えても良い。 By coupling the diazo component and the coupler component thus obtained in the presence of the fatty acid ester according to a conventional method, C.I. I. An aqueous suspension of Pigment Yellow 14 can be prepared. At this time, the coupler component may be added to the diazo component, or the diazo component may be added to the coupler component, but the coupler component and the diazo component may be added to water.
前記脂肪酸エステルの存在下で、3,3´−ジクロロベンジジンのテトラゾニウム塩とアセト酢酸−o−トルイダイドとをカップリングさせてC.I.ピグメントイエロー14を製造すると、顔料分子の生成時に前記脂肪酸エステルが存在する結果、フロック外部の顔料分子のみならず、フロック内部の顔料分子にも前記脂肪酸エステルが充分に吸着される結果、水性インキや水性塗料の調製時の分散において、微細な粒子径となった際にも、優れた分散性、分散安定性を発揮することが出来る。 In the presence of the fatty acid ester, a tetrazonium salt of 3,3′-dichlorobenzidine and acetoacetic acid-o-toluidide were coupled to form C.I. I. When Pigment Yellow 14 is produced, the fatty acid ester is present when the pigment molecule is formed. As a result, the fatty acid ester is sufficiently adsorbed not only by the pigment molecule outside the flock but also by the pigment molecule inside the flock. In the dispersion during the preparation of the water-based paint, excellent dispersibility and dispersion stability can be exhibited even when the particle size becomes fine.
前記脂肪酸エステルの存在下で、3,3´−ジクロロベンジジンのテトラゾニウム塩とアセト酢酸−o−トルイダイドとをカップリングさせる方法としては、例えば、カップリング反応を行う原料自身である、3,3´−ジクロロベンジジンのテトラゾニウム塩、アセト酢酸−o−トルイダイド又はこれら両方に含有させておき、いずれか一方を他方と混合し反応させる方法もあるが、前記脂肪酸エステルを含有する水中に、3,3´−ジクロロベンジジンのテトラゾニウム塩とアセト酢酸−o−トルイダイドとを加えてカップリングさせる方法が、一次粒子が出来る傍からジスアゾ顔料の表面を被覆することが出来、より優れた分散性、分散安定性を達成することが出来るので好ましい。 As a method for coupling 3,3′-dichlorobenzidine tetrazonium salt and acetoacetic acid-o-toluidide in the presence of the fatty acid ester, for example, 3,3 ′, which is a raw material for performing a coupling reaction, is used. -There is also a method in which a tetrazonium salt of dichlorobenzidine, acetoacetic acid-o-toluidide, or both of these are mixed and reacted with the other, but in the water containing the fatty acid ester, 3, 3 ' -The method of coupling by adding the tetrazonium salt of dichlorobenzidine and acetoacetic acid-o-toluidide can coat the surface of disazo pigment from the side where primary particles are formed, and has better dispersibility and dispersion stability. This is preferable because it can be achieved.
尚、カップリング反応を行うために併用することが出来る緩衝剤は、例えば酢酸ナトリウム等の系内合成により、調製出来る。緩衝剤は、pH4〜6に調整されたものであることが好ましい。水に対してカップラー成分とジアゾ成分とを加えてカップリング反応を行う場合には、緩衝剤が好適には併用される。 In addition, the buffer which can be used together in order to perform a coupling reaction can be prepared by, for example, in-system synthesis such as sodium acetate. The buffer is preferably adjusted to pH 4-6. In the case of performing a coupling reaction by adding a coupler component and a diazo component to water, a buffering agent is preferably used in combination.
カップリング反応によりジスアゾ顔料を得るための反応条件は、公知慣用の条件に従えばよく、特に制限されるものではないが、通常、温度0〜30℃で時間は30分〜3時間にて行うことが出来る。 The reaction conditions for obtaining the disazo pigment by the coupling reaction may be in accordance with known and usual conditions, and are not particularly limited, but are usually performed at a temperature of 0 to 30 ° C. for 30 minutes to 3 hours. I can do it.
C.I.ピグメントイエロー14と前記脂肪酸エステルとを必須成分として含有するジスアゾ顔料水懸濁液は、必要に応じてpH調整を行った上で、常法に従って、例えば50℃以上沸点未満好ましくは70℃〜沸点未満で所定時間加熱して熟成等を行うことで、顔料粒子の粒子径や分布等の調整を行うことが出来る。加熱時間は特に制限されるものではないが、例えば、30分〜5時間好ましくは45分〜3時間である。この様な加熱熟成は、pH9〜12に調整したジスアゾ顔料水懸濁液に対して行うことが好ましい。この際、アルカリ性での熟成を行うことで、フロック外部の酸のみならず、フロック内部の酸をも中和して塩の形とすることが出来、さらにアルカリ性とすることで、後記する特にカルボキシル基を含有する皮膜形成性樹脂と塩基性化合物とを組み合わせて用いた水性インキや水性塗料の保存安定性等を高めることが出来るので、好ましい。 C. I. The disazo pigment aqueous suspension containing Pigment Yellow 14 and the fatty acid ester as essential components is adjusted for pH as necessary, and is, for example, 50 ° C. or higher and lower than boiling point, preferably 70 ° C. to boiling point, according to a conventional method. The particle size, distribution, etc. of the pigment particles can be adjusted by heating for less than a predetermined time and aging. The heating time is not particularly limited, but is, for example, 30 minutes to 5 hours, preferably 45 minutes to 3 hours. Such heat aging is preferably performed on the aqueous suspension of the disazo pigment adjusted to pH 9-12. At this time, by aging with alkalinity, not only the acid outside the floc but also the acid inside the floc can be neutralized into a salt form, and further alkaline, This is preferable because the storage stability of a water-based ink or water-based paint using a combination of a film-forming resin containing a group and a basic compound can be improved.
尚、このアルカリ性での加熱熟成は、後記する濾過洗浄と相俟って、得られるジスアゾ顔料組成物を日本工業規格JIS K 5101−17−1に定めるpH値8〜11とする最も有力な手段である。 This alkaline heat aging, combined with filtration washing described later, is the most effective means for setting the resulting disazo pigment composition to a pH value of 8 to 11 as defined in Japanese Industrial Standard JIS K 5101-17-1. It is.
熟成を経たジスアゾ顔料水懸濁液は、濾過や水洗することで、ウエットケーキやスラリー等の湿潤状態のジスアゾ顔料組成物とすることが出来る。濾過と水洗を繰り返すことで熟成時よりもpHを下げ、中性寄りのアルカリ性とすることが出来、精製をも行うことも出来る。これら水洗に当たっては、湯を用いても良いし、必要ならアルカリの希薄水溶液を用いても良い。顔料粒子内外に含まれる酸は、確実に中和して塩の形としておくことが、後記する水性インキや水性塗料中における顔料粒子の分散安定性等をより高める上では好ましい。 The aqueous suspension of the disazo pigment that has undergone aging can be made into a wet disazo pigment composition such as a wet cake or slurry by filtering or washing with water. By repeating filtration and washing with water, the pH can be lowered compared to that at the time of ripening, and the pH can be neutralized, and purification can also be performed. In washing with water, hot water may be used, or an alkaline dilute aqueous solution may be used if necessary. It is preferable that the acid contained inside and outside the pigment particles is surely neutralized to be in the form of a salt in order to further improve the dispersion stability of the pigment particles in a water-based ink or water-based paint described later.
湿潤状態のジスアゾ顔料組成物を乾燥することで、パウダーやグラニュール等の乾燥状態のジスアゾ顔料組成物とすることが出来る。ランプ状となった乾燥状態のジスアゾ顔料組成物は、解砕により解すことも出来る。また乾燥状態のジスアゾ顔料組成物は、分級を行うことでより粒度分布を狭くすることも出来る。 By drying the disazo pigment composition in a wet state, a disazo pigment composition in a dry state such as powder or granule can be obtained. The dried disazo pigment composition in the form of a lamp can also be pulverized. In addition, the disazo pigment composition in a dry state can be narrowed in particle size distribution by classification.
本発明のジスアゾ顔料組成物は、公知慣用の各種用途、例えば、平版印刷インキ、グラビア印刷インキ、フレキソ印刷インキの様な印刷インキ、塗料、着色プラスチック成形品等の汎用用途、静電荷像現像用トナー、カラーフィルター、インクジェット記録用水性インク等のハイテク用途に適用することが出来る。 The disazo pigment composition of the present invention is used in various known and conventional applications, for example, printing inks such as lithographic printing inks, gravure printing inks, flexographic printing inks, paints, colored plastic molded products, etc., for electrostatic image development It can be applied to high-tech applications such as toners, color filters, and water-based inks for ink jet recording.
本発明のジスアゾ顔料組成物は、C.I.ピグメントイエロー14を主成分としてより親水性に優れる前記脂肪酸エステルを含有しているので、なかでも特に水性インキ又は水性塗料の調製に適している。 The disazo pigment composition of the present invention comprises C.I. I. Since the fatty acid ester having pigment yellow 14 as a main component and more excellent in hydrophilicity is contained, it is particularly suitable for the preparation of water-based ink or water-based paint.
本発明のジスアゾ顔料組成物と水性ビヒクルとからは、水性インキや水性塗料を好適に調製することが出来る。この水性ビヒクルは、溶媒が揮散した際に、顔料を基材上に定着固着させるための皮膜形成性樹脂と、溶媒としての水とを、主として含有する。尚、水性とは液媒体が水のみか水を質量換算で60%以上含有する液媒体を言う。 From the disazo pigment composition of the present invention and an aqueous vehicle, aqueous inks and aqueous paints can be suitably prepared. This aqueous vehicle mainly contains a film-forming resin for fixing and fixing a pigment on a substrate when the solvent is volatilized, and water as a solvent. In addition, aqueous | water-based means the liquid medium in which a liquid medium contains only water or 60% or more of water by mass conversion.
水性インキを調製するための皮膜形成性樹脂としては、例えば、ポリアミド樹脂、スチレン樹脂、マレイン酸樹脂、アクリル樹脂、ニトロセルロース、エチルセルロース、酢酸セルロース、エチレン−酢酸ビニル共重合体樹脂、ポリウレタン樹脂、ポリエステル樹脂等の水溶性か水分散性の樹脂一種又はこれら二種以上の混合物が挙げられる。 Examples of film-forming resins for preparing water-based inks include polyamide resins, styrene resins, maleic resins, acrylic resins, nitrocellulose, ethyl cellulose, cellulose acetate, ethylene-vinyl acetate copolymer resins, polyurethane resins, and polyesters. A water-soluble or water-dispersible resin such as a resin or a mixture of two or more of these may be mentioned.
カルボキシル基を含有する皮膜形成性樹脂と塩基性化合物とを組み合わせて用いると、水に対して皮膜形成性樹脂が安定的に溶解又は分散した水性ビヒクルが出来る。塩基性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニアの様な無機塩基、ジエチルアミン、トリエチルアミン、ジエタノールアミン等の有機塩基が挙げられる。水性インキを調製するための好適な水性ビヒクルは、塩基性化合物と、皮膜形成性樹脂としてスチレン−(メタ)アクリル酸エステル−(メタ)アクリル酸共重合体を含有する。 When a film-forming resin containing a carboxyl group and a basic compound are used in combination, an aqueous vehicle in which the film-forming resin is stably dissolved or dispersed in water can be formed. Examples of the basic compound include inorganic bases such as sodium hydroxide, potassium hydroxide and ammonia, and organic bases such as diethylamine, triethylamine and diethanolamine. A suitable aqueous vehicle for preparing an aqueous ink contains a basic compound and a styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer as a film-forming resin.
水性インキは、本発明のジスアゾ顔料組成物と水性ビヒクルと水、更に、その他の親水性有機溶剤、体質顔料、補助剤等とを混合することにより調製することが出来る。 The water-based ink can be prepared by mixing the disazo pigment composition of the present invention, the water-based vehicle, water, and other hydrophilic organic solvent, extender pigment, auxiliary agent and the like.
親水性有機溶剤としては、例えば、エタノール、メタノール、イソプロパノール(IPA)、アセトン、酢酸エチル、乳酸エチル、セロソルブ、ジアセトンアルコール等が挙げられる。体質顔料としては、例えば、硫酸バリウム、炭酸バリウム、炭酸カルシウム、シリカ、タルク、ケイ酸カルシウム、沈降性炭酸マグネシウム等が挙げられる。その他の補助剤としては、例えば、ワックス、界面活性剤、消泡剤、可塑剤、紫外線防止剤、酸化防止剤、帯電防止剤等が挙げられる。 Examples of the hydrophilic organic solvent include ethanol, methanol, isopropanol (IPA), acetone, ethyl acetate, ethyl lactate, cellosolve, diacetone alcohol and the like. Examples of extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, talc, calcium silicate, and precipitated magnesium carbonate. Examples of other auxiliary agents include waxes, surfactants, antifoaming agents, plasticizers, ultraviolet inhibitors, antioxidants, antistatic agents and the like.
水性塗料も概ね水性インキと同様にして調製することが出来る。
水性塗料を調製するための皮膜形成性樹脂としては、前記した樹脂の他、アルキド樹脂、シリコーン樹脂、フッ素樹脂等が挙げられる。塗膜強度を増すために、皮膜形成性樹脂に硬化剤を併用することが出来る。この様な硬化剤としては、例えば、メラミン樹脂、ユリア樹脂、ポリイソシアネート等が挙げられる。また補助剤として用いる増粘剤としては、例えば、カルボキシメチルセルロース、ポリビニルピロリドン、ポリビニルアルコール等が挙げられる。
Water-based paints can be prepared in substantially the same manner as water-based inks.
Examples of the film-forming resin for preparing the water-based paint include alkyd resins, silicone resins, fluororesins and the like in addition to the above-described resins. In order to increase the coating strength, a curing agent can be used in combination with the film-forming resin. Examples of such a curing agent include melamine resin, urea resin, polyisocyanate, and the like. Moreover, as a thickener used as an adjuvant, carboxymethylcellulose, polyvinylpyrrolidone, polyvinyl alcohol, etc. are mentioned, for example.
水性インキや水性塗料は、質量換算で、例えば、皮膜形成性樹脂10〜50部、水を含む液媒体30〜80部、本発明のジスアゾ顔料組成物1〜25部を用いて、必要に応じて補助剤を含めて全体が100部となる様に、そして印刷や塗装に適した低粘度となる様に調製することが出来る。 The water-based ink and the water-based paint are, in terms of mass, for example, 10 to 50 parts of a film-forming resin, 30 to 80 parts of a liquid medium containing water, and 1 to 25 parts of the disazo pigment composition of the present invention. Thus, it can be prepared so that the total amount including the adjuvant becomes 100 parts and low viscosity suitable for printing and painting.
こうして得られた黄色の水性インキは、公知慣用の紅色や藍色の水性インキと組み合わせて、減法混色により中間色やフルカラーの画像を印刷することが出来る。 The yellow water-based ink thus obtained can be used in combination with known and commonly used red or indigo water-based inks to print intermediate or full-color images by subtractive color mixing.
以下に実施例、比較例を挙げ、本発明を更に詳細に説明するが、本発明は、これにより限定されるものではない。尚、例中の部及び%は、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, the part and% in an example are a mass reference | standard.
3,3′−ジクロロベンジジン二塩酸塩(固形分100%)300部1.186モルを水1000部中に撹拌下投入し、同時に35%塩酸371部を仕込む。氷と水で、液量と温度を調整する。30%亜硝酸ソーダ559部を投入し、テトラゾ化する。過剰の亜硝酸をスルファミン酸で消去し、濾過後の液をテトラゾニウム塩を含有する溶液とする(ジアゾ成分の水溶液)。
別にカップラーとしてアセト酢酸−o−トルイダイド476部を2500部の水中に分散させ、20%苛性ソーダで溶解し、カップラー成分の水溶液とする。
別途準備したカップリング反応用の容器に水10,000部を入れ、80%酢酸の53部とレオドールTW−O120V(花王株式会社ポリオキシエチレンソルビタンモノオレート。HLB=15.0 ポリオキシエチレンの繰り返し単位の合計は、15〜30。)23部を加え、撹拌混合する。次に、カップラー成分の水溶液の投入を開始し、酢酸ナトリウム緩衝液を作成後、pH5、温度20℃の管理下で、前記各成分の水溶液を同時に滴下し、カップリング反応を行い、顔料組成物を合成した。
顔料合成後、20%苛性ソーダ投入で、顔料スラリーのpHをpH10に調整した。昇温し、90℃で60分間の保温を行い、アルカリ熟成を行った。
出来上がった顔料スラリーを濾過操作し、水洗浄した顔料ウエットケーキを分離した。単離した顔料ウエットケーキを110℃で乾燥し、乾燥したランプをジューサーで粉砕し、黄色の顔料組成物の粉末を得た。
尚、この顔料組成物について、日本工業規格JIS K5101−17−1により、抽出液のpHを測定したところ、pH8.8であった。
1.186 mol of 300 parts of 3,3′-dichlorobenzidine dihydrochloride (solid content: 100%) is charged into 1000 parts of water with stirring, and 371 parts of 35% hydrochloric acid are charged at the same time. Adjust the volume and temperature with ice and water. 559 parts of 30% sodium nitrite is added and tetrazotized. Excess nitrous acid is eliminated with sulfamic acid, and the solution after filtration is made into a solution containing a tetrazonium salt (an aqueous solution of a diazo component).
Separately, 476 parts of acetoacetic acid-o-toluidide as a coupler is dispersed in 2500 parts of water and dissolved with 20% caustic soda to obtain an aqueous solution of the coupler component.
Put 10,000 parts of water in a separately prepared container for coupling reaction, 53 parts of 80% acetic acid and Rheodor TW-O120V (Kao Co., Ltd. polyoxyethylene sorbitan monooleate. HLB = 15.0 Repeat of polyoxyethylene The total number of units is 15-30.) Add 23 parts and stir and mix. Next, the addition of the aqueous solution of the coupler component is started, and after preparing a sodium acetate buffer solution, the aqueous solution of each component is simultaneously added dropwise under the control of pH 5 and temperature of 20 ° C., and a coupling reaction is performed, whereby the pigment composition Was synthesized.
After pigment synthesis, the pH of the pigment slurry was adjusted to pH 10 by adding 20% sodium hydroxide. The temperature was raised, the temperature was kept at 90 ° C. for 60 minutes, and alkali aging was performed.
The finished pigment slurry was filtered to separate a water-washed pigment wet cake. The isolated pigment wet cake was dried at 110 ° C., and the dried lamp was pulverized with a juicer to obtain a powder of a yellow pigment composition.
In addition, about this pigment composition, it was pH 8.8 when pH of the extract was measured by Japanese Industrial Standard JIS K5101-17-1.
上記実施例1と同様に、ジアゾ化液とカップラー溶液と各々を別個に作製した。
カップリング反応容器中には、実施例1のレオドールTW−O120V(花王株式会社)に代えて、レオドールスーパーSP−L10(花王株式会社ソルビタンモノラウレート。HLB=8.6)の同量を用い、それ以外の操作は、全て実施例1と同様に実施し、黄色の顔料組成物の粉末を得た。
尚、この顔料組成物について、JIS K5101−17−1により、抽出液のpHを測定したところ、pH9.0であった。
Similarly to Example 1, the diazotization liquid and the coupler solution were separately prepared.
In the coupling reaction vessel, the same amount of Rhedol Super SP-L10 (Kao Corporation sorbitan monolaurate, HLB = 8.6) was used instead of Rheodor TW-O120V (Kao Corporation) of Example 1. All other operations were carried out in the same manner as in Example 1 to obtain a yellow pigment composition powder.
For this pigment composition, the pH of the extract was measured according to JIS K5101-17-1 and found to be pH 9.0.
[比較例1]
上記実施例1と同様に、ジアゾ化液とカップラー溶液と各々を別個に作製した。
カップリング反応用の容器には、水10,000部と80%酢酸53部だけを用意し、それ以降の操作は、全て実施例1と同様に実施し、黄色のC.I.ピグメントイエロー14顔料を得た。
尚、この顔料組成物について、日本工業規格JIS K5101−17−1により、抽出液のpHを測定したところ、pH8.5であった。
[Comparative Example 1]
Similarly to Example 1, the diazotization liquid and the coupler solution were separately prepared.
In the container for the coupling reaction, only 10,000 parts of water and 53 parts of 80% acetic acid were prepared, and the subsequent operations were all carried out in the same manner as in Example 1, and the yellow C.I. I. Pigment Yellow 14 pigment was obtained.
In addition, about this pigment composition, when pH of the extract was measured according to Japanese Industrial Standard JIS K5101-17-1, it was pH8.5.
[比較例2]
上記実施例2と同様の操作をカップリング反応後の顔料スラリー合成まで実施する。
pH10への調整は行わず、pH5で、昇温を開始し、90℃で60分間の保温を行い、濾過以降の操作は、実施例1と同様に実施し、黄色の顔料組成物を得た。
尚、この顔料組成物について、日本工業規格JIS K5101−17−1により、抽出液のpHを測定したところ、pH5.5であった。
[Comparative Example 2]
The same operation as in Example 2 is performed until the pigment slurry synthesis after the coupling reaction.
Adjustment to pH 10 was not performed, the temperature increase was started at pH 5, and the temperature was kept at 90 ° C. for 60 minutes. The operation after filtration was performed in the same manner as in Example 1 to obtain a yellow pigment composition. .
In addition, about this pigment composition, when pH of the extract was measured according to Japanese Industrial Standard JIS K5101-17-1, it was pH 5.5.
[比較例3]
上記実施例2と同様に、顔料スラリーの合成まで実施し、pH10への調整は行わず、pH5の顔料スラリーにレオドールスーパーSP−L10の23部を添加し、昇温を開始する。以降の操作は、全て実施例2と同様に実施し、黄色の顔料組成物を得た。
尚、この顔料組成物について、日本工業規格JIS K5101−17−1により、抽出液のPHを測定したところ、pH6.0であった。
[Comparative Example 3]
In the same manner as in Example 2 above, the synthesis is performed until the synthesis of the pigment slurry, and the pH is not adjusted, but 23 parts of Rhedol Super SP-L10 is added to the pigment slurry of pH 5, and the temperature is increased. All subsequent operations were performed in the same manner as in Example 2 to obtain a yellow pigment composition.
With respect to this pigment composition, the pH of the extract was measured according to Japanese Industrial Standard JIS K5101-17-1, and it was pH 6.0.
[比較例4]
上記実施例1と同様に、ジアゾ化液とカップラー溶液と各々を別個に作製した。
カップリング反応容器中には、実施例1のレオドールTW−O120V(花王株式会社)に代えて、ノイゲンET−102(第一工業製薬株式会社ポリオキシエチレンラウリルエーテル)の同量を用い、それ以外の操作は、全て実施例1と同様に実施し、黄色の顔料組成物の粉末を得た。
尚、この顔料組成物について、日本工業規格JIS K5101−17−1により、抽出液のpHを測定したところ、pH9.1であった。
[Comparative Example 4]
Similarly to Example 1, the diazotization liquid and the coupler solution were separately prepared.
In the coupling reaction vessel, the same amount of Neugen ET-102 (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether) was used instead of Rheodor TW-O120V (Kao Corporation) of Example 1, and the others. These operations were all carried out in the same manner as in Example 1 to obtain a yellow pigment composition powder.
In addition, about this pigment composition, when pH of the extract was measured according to Japanese Industrial Standard JIS K5101-17-1, it was pH 9.1.
[比較例5]
上記実施例2と同様に、顔料スラリーの合成まで実施し、pH10への調整は行わず、pH5の顔料スラリーにエマノーンCH−80(花王株式会社ポリオキシエチレン硬化ひまし油)の23部を添加し、昇温を開始する。以降の操作は、全て実施例1と同様に実施し、黄色の顔料組成物を得た。
尚、この顔料組成物について、日本工業規格JIS K5101−17−1により、抽出液のpHを測定したところ、pH5.6であった。
[Comparative Example 5]
In the same manner as in Example 2 above, the synthesis was performed until the pigment slurry was synthesized, and adjustment to pH 10 was not performed. 23 parts of Emanon CH-80 (Kao Co., Ltd. polyoxyethylene hydrogenated castor oil) was added to the pigment slurry at pH 5, Start heating up. All subsequent operations were carried out in the same manner as in Example 1 to obtain a yellow pigment composition.
In addition, about this pigment composition, it was pH5.6 when pH of the extract was measured by Japanese Industrial Standard JISK5101-17-1.
水性グラビア印刷インキの作製方法
実施例1〜2及び比較例1〜5で得られた各粉末顔料組成物16部と練肉ニス〔ジョンソンポリマー(株)製ジョンクリル(登録商標)61J/蒸留水/IPA=30/30/5(質量比)混合品〕38部と3mmガラスビーズ160部とを250mlポリビンに秤量し、東洋精機(株)製ペイントコンディショナーで、60分間分散する。ジョンソンポリマー(株)製ジョンクリル(登録商標)74Jの84部を追加し、5分間分散し、水性グラビア印刷インキ(以下、原色インキと称す。)を得た。実施例のインキは、いずれも発泡が少なく調製がしやすかった。
一方、100mlポリビンに、ダイフレックス アスティア(登録商標)D250〔大日本インキ化学工業(株)製白インキ〕白20部と上記の原色インキ4部を秤量し、30分間上記ペイントコンディショナーで混合インキ(以下、淡色インキと称す。)を得た。
Preparation method of aqueous gravure printing ink 16 parts of each powder pigment composition obtained in Examples 1 and 2 and Comparative Examples 1 to 5 and paste meat varnish [John Crill (registered trademark) 61J / Johnson Polymer Co., Ltd./distilled water] / IPA = 30/30/5 (mass ratio) mixed product] 38 parts and 160 parts of 3 mm glass beads are weighed in a 250 ml polybin, and dispersed for 60 minutes with a paint conditioner manufactured by Toyo Seiki Co., Ltd. 84 parts of John Crill (registered trademark) 74J manufactured by Johnson Polymer Co., Ltd. was added and dispersed for 5 minutes to obtain an aqueous gravure printing ink (hereinafter referred to as primary color ink). The inks of the examples were easy to prepare with little foaming.
On the other hand, in a 100 ml polybin, 20 parts of Daiflex Astia (registered trademark) D250 [white ink manufactured by Dainippon Ink & Chemicals, Inc.] and 4 parts of the above primary color ink are weighed and mixed with the above paint conditioner for 30 minutes. Hereinafter, this is referred to as light color ink.).
評価方法(光沢、透明性、着色力)
黒地付アート紙に、No.6バーコーターで、原色インキを展色し、自然乾燥後、グレタグ社製グレタグ濃度計SPL50とデータカラー社製分光光度計マイクロフラッシュ200dとBYK−Chemie Japan社製の光沢計(60°光沢)で展色表面を測定する。同様に、淡色インキも展色し、分光光度計で着色力を測定した。その結果を表1に示した。
尚、着色力については、比較例1の顔料組成物から調製したインキにおける印刷画像の着色力を100%とした場合の各インキの着色力を表示した。透明性は、アート紙の黒地展色面を測定し、B値が大きいと透明性が大である。
Evaluation method (gloss, transparency, tinting strength)
On art paper with black background, No. With a 6 bar coater, the primary color ink is developed, and after natural drying, the Gretag density meter SPL50 manufactured by Gretag, the spectrophotometer Microflash 200d manufactured by Datacolor, and the gloss meter (60 ° gloss) manufactured by BYK-Chemie Japan are used. Measure the color development surface. Similarly, light-colored ink was also developed and the coloring power was measured with a spectrophotometer. The results are shown in Table 1.
In addition, about the coloring power, the coloring power of each ink when the coloring power of the printed image in the ink prepared from the pigment composition of the comparative example 1 was made into 100% was displayed. Transparency is high when the black color of art paper is measured and the B value is large.
尚、実施例1及び2の顔料組成物を用いて水性グラビア印刷インキを調製しようとしたところ、比較例2〜5の顔料組成物を用いて水性グラビア印刷インキを調製しようとした場合に比べて、発泡は抑制されていた。実施例1の顔料組成物を用いて調製された水性グラビア印刷インキで、実印刷を行ったところ、実施例2の顔料組成物を用いて調製された水性グラビア印刷インキよりも、版かぶり適性とラミネート強度は、著しく優れていた。 In addition, when it was going to prepare water-based gravure printing ink using the pigment composition of Example 1 and 2, compared with the case where it was going to prepare water-based gravure printing ink using the pigment composition of Comparative Examples 2-5. The foaming was suppressed. When actual printing was performed with the aqueous gravure printing ink prepared using the pigment composition of Example 1, it was more suitable for plate fogging than the aqueous gravure printing ink prepared using the pigment composition of Example 2. The laminate strength was remarkably excellent.
本発明の実施例1の顔料組成物を用いて調製された水性グラビア印刷インキは、界面活性剤を用いずに製造された比較例1の顔料組成物やポリオキシエチレンラウリルエーテルを用いて製造された比較例4の顔料組成物から各々調製された水性グラビア印刷インキに比べて、光沢は勿論のこと、透明性及び着色力のいずれにも格段に優れていることが明らかである。
ポリオキシエチレンソルビタン脂肪酸エステルを用いて製造された実施例1の顔料組成物から調製された水性グラビア印刷インキは、ソルビタン脂肪酸エステルを同様に用いて製造された実施例2の顔料組成物から調製された水性グラビア印刷インキに比べて、光沢は勿論のこと、透明性及び着色力のいずれにおいてもより優れていることが明らかである。
加熱熟成をアルカリ性にて行ったJIS K5101−17−1におけるpHがより高い領域にある実施例2の顔料組成物から調製された水性グラビア印刷インキは、pH調整を行わずに通常通りに加熱熟成したJIS K5101−17−1におけるpHがより低い比較例2、比較例3及び比較例同5の顔料組成物から調製された水性グラビア印刷インキに比べて、着色力においてより優れていることが明らかである。
The aqueous gravure printing ink prepared using the pigment composition of Example 1 of the present invention was manufactured using the pigment composition of Comparative Example 1 and polyoxyethylene lauryl ether manufactured without using a surfactant. In addition, it is clear that both the gloss and the transparency and coloring power are remarkably superior to the aqueous gravure printing inks prepared from the pigment composition of Comparative Example 4, respectively.
An aqueous gravure printing ink prepared from the pigment composition of Example 1 prepared using polyoxyethylene sorbitan fatty acid ester was prepared from the pigment composition of Example 2 prepared using sorbitan fatty acid ester as well. It is clear that the water-based gravure printing ink is superior not only in gloss but also in transparency and coloring power.
The aqueous gravure printing ink prepared from the pigment composition of Example 2 in the region where the pH is higher in JIS K5101-17-1, in which the heat aging was performed with alkalinity, was heat aging as usual without adjusting the pH. It is clear that the coloring power is superior to the aqueous gravure printing inks prepared from the pigment compositions of Comparative Example 2, Comparative Example 3 and Comparative Example 5 having a lower pH in JIS K5101-17-1. It is.
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