JP2012062375A - Method for producing disazo pigment composition and printing ink composition - Google Patents
Method for producing disazo pigment composition and printing ink composition Download PDFInfo
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- JP2012062375A JP2012062375A JP2010206196A JP2010206196A JP2012062375A JP 2012062375 A JP2012062375 A JP 2012062375A JP 2010206196 A JP2010206196 A JP 2010206196A JP 2010206196 A JP2010206196 A JP 2010206196A JP 2012062375 A JP2012062375 A JP 2012062375A
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- Prior art keywords
- coupler
- solution
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- tetrazo
- acid
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- 239000000049 pigment Substances 0.000 title claims abstract description 94
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 title claims abstract description 44
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000005859 coupling reaction Methods 0.000 claims abstract description 26
- 125000001424 substituent group Chemical group 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 166
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 claims description 18
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- -1 alkali metal salt Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 238000010586 diagram Methods 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 150000007656 barbituric acids Chemical class 0.000 abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 57
- 239000000976 ink Substances 0.000 description 48
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 40
- 238000002347 injection Methods 0.000 description 30
- 239000007924 injection Substances 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 238000000034 method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004040 coloring Methods 0.000 description 21
- 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 20
- 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 20
- 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 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 18
- 239000002002 slurry Substances 0.000 description 15
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 14
- 238000010168 coupling process Methods 0.000 description 14
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 14
- 230000008878 coupling Effects 0.000 description 13
- 239000003981 vehicle Substances 0.000 description 13
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- QINYBRXZAIWZBM-UHFFFAOYSA-N 2-(3-oxobutanoylamino)benzoic acid Chemical class CC(=O)CC(=O)NC1=CC=CC=C1C(O)=O QINYBRXZAIWZBM-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 238000011010 flushing procedure Methods 0.000 description 8
- HXFNXEIKMAEASE-UHFFFAOYSA-N 4-(4-amino-3-chlorophenyl)-2-chloroaniline;hydrochloride Chemical compound Cl.C1=C(Cl)C(N)=CC=C1C1=CC=C(N)C(Cl)=C1 HXFNXEIKMAEASE-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 235000010288 sodium nitrite Nutrition 0.000 description 7
- UYLOXJPHSAEEAB-UHFFFAOYSA-N OC1=C(C=C(C(=O)O)C=C1)NC(CC(=O)C)=O Chemical compound OC1=C(C=C(C(=O)O)C=C1)NC(CC(=O)C)=O UYLOXJPHSAEEAB-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IHBUIRYUIBNXKI-UHFFFAOYSA-N 2-(3-oxobutanoylamino)benzamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(N)=O IHBUIRYUIBNXKI-UHFFFAOYSA-N 0.000 description 4
- OSHMIKIYRAREFA-UHFFFAOYSA-N 4-(3-oxobutanoylamino)benzamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C(N)=O)C=C1 OSHMIKIYRAREFA-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VVSASNKOFCZVES-UHFFFAOYSA-N 1,3-dimethyl-1,3-diazinane-2,4,6-trione Chemical compound CN1C(=O)CC(=O)N(C)C1=O VVSASNKOFCZVES-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- VABIRXFGIDBUSW-UHFFFAOYSA-N 2-(3-oxobutanoylamino)terephthalic acid Chemical compound CC(=O)CC(=O)NC1=CC(C(O)=O)=CC=C1C(O)=O VABIRXFGIDBUSW-UHFFFAOYSA-N 0.000 description 2
- UFQVIQVSYSXYAJ-UHFFFAOYSA-N 2-methyl-4-(3-oxobutanoylamino)benzenesulfonic acid Chemical compound CC(=O)CC(=O)NC1=CC=C(S(O)(=O)=O)C(C)=C1 UFQVIQVSYSXYAJ-UHFFFAOYSA-N 0.000 description 2
- CYXMXIQEXZFYRD-UHFFFAOYSA-N 3-chloro-4-methyl-2-(3-oxobutanoylamino)benzenesulfonic acid Chemical compound CC(=O)CC(=O)NC1=C(Cl)C(C)=CC=C1S(O)(=O)=O CYXMXIQEXZFYRD-UHFFFAOYSA-N 0.000 description 2
- GRLSWESXIFWOBF-UHFFFAOYSA-N 4-(3-oxobutanoylamino)benzenesulfonic acid Chemical compound CC(=O)CC(=O)NC1=CC=C(S(O)(=O)=O)C=C1 GRLSWESXIFWOBF-UHFFFAOYSA-N 0.000 description 2
- NTVPMGIWCMTNMD-UHFFFAOYSA-N 4-(3-oxobutanoylamino)benzoic acid Chemical class CC(=O)CC(=O)NC1=CC=C(C(O)=O)C=C1 NTVPMGIWCMTNMD-UHFFFAOYSA-N 0.000 description 2
- FZYYBUMFEULWKY-UHFFFAOYSA-N OC=1C=C(C(=O)O)C=CC1NC(CC(=O)C)=O Chemical class OC=1C=C(C(=O)O)C=CC1NC(CC(=O)C)=O FZYYBUMFEULWKY-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- HOFBJJVRJFTXGF-UHFFFAOYSA-N n-(2-hydroxyphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1O HOFBJJVRJFTXGF-UHFFFAOYSA-N 0.000 description 2
- MOUVJGIRLPZEES-UHFFFAOYSA-N n-(4-chloro-2,5-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(NC(=O)CC(C)=O)=C(OC)C=C1Cl MOUVJGIRLPZEES-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- SHBTUGJAKBRBBJ-UHFFFAOYSA-N 1,3-diethyl-2-sulfanylidene-1,3-diazinane-4,6-dione Chemical compound CCN1C(=O)CC(=O)N(CC)C1=S SHBTUGJAKBRBBJ-UHFFFAOYSA-N 0.000 description 1
- UXOXUHMFQZEAFR-UHFFFAOYSA-N 2,2',5,5'-Tetrachlorobenzidine Chemical compound C1=C(Cl)C(N)=CC(Cl)=C1C1=CC(Cl)=C(N)C=C1Cl UXOXUHMFQZEAFR-UHFFFAOYSA-N 0.000 description 1
- IPOXVWBIYJPKII-UHFFFAOYSA-N 2-(3-oxobutanoyl)benzamide Chemical group C(CC(=O)C)(=O)C1=C(C(=O)N)C=CC=C1 IPOXVWBIYJPKII-UHFFFAOYSA-N 0.000 description 1
- SNXGSPZWYIUBID-UHFFFAOYSA-N 2-acetamido-6-methoxybenzoic acid Chemical compound COC1=CC=CC(NC(C)=O)=C1C(O)=O SNXGSPZWYIUBID-UHFFFAOYSA-N 0.000 description 1
- NFSOOPQRTBEFDR-UHFFFAOYSA-N 2-amino-5-(4-amino-3-sulfophenyl)benzenesulfonic acid Chemical compound C1=C(S(O)(=O)=O)C(N)=CC=C1C1=CC=C(N)C(S(O)(=O)=O)=C1 NFSOOPQRTBEFDR-UHFFFAOYSA-N 0.000 description 1
- GZUCOCDWGQMOKH-UHFFFAOYSA-N 2-hydroxy-5-(3-oxobutanoylamino)benzoic acid Chemical compound CC(=O)CC(=O)NC1=CC=C(O)C(C(O)=O)=C1 GZUCOCDWGQMOKH-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- RVBUGGBMJDPOST-UHFFFAOYSA-N 2-thiobarbituric acid Chemical compound O=C1CC(=O)NC(=S)N1 RVBUGGBMJDPOST-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NWVZTUUHTHEEIY-UHFFFAOYSA-N 3,5-dichloro-2-(3-oxobutanoylamino)benzenesulfonic acid Chemical compound CC(=O)CC(=O)NC1=C(Cl)C=C(Cl)C=C1S(O)(=O)=O NWVZTUUHTHEEIY-UHFFFAOYSA-N 0.000 description 1
- PUMBCOJMQGIIEW-UHFFFAOYSA-N 3-(3-oxobutanoylamino)benzenesulfonic acid Chemical compound CC(=O)CC(=O)NC1=CC=CC(S(O)(=O)=O)=C1 PUMBCOJMQGIIEW-UHFFFAOYSA-N 0.000 description 1
- YYBMBANDPSFUPG-UHFFFAOYSA-N 3-chloro-4-(3-oxobutanoyl)benzoic acid Chemical class ClC=1C=C(C(=O)O)C=CC=1C(CC(=O)C)=O YYBMBANDPSFUPG-UHFFFAOYSA-N 0.000 description 1
- FCYAKOWBDZOBTK-UHFFFAOYSA-N 3-methoxy-2-methyl-4-(3-oxobutanoylamino)benzenesulfonic acid Chemical compound COC1=C(C)C(S(O)(=O)=O)=CC=C1NC(=O)CC(C)=O FCYAKOWBDZOBTK-UHFFFAOYSA-N 0.000 description 1
- XEWFWIVHLHQTLK-UHFFFAOYSA-N 3-methyl-4-(3-oxobutanoyl)benzoic acid Chemical class CC=1C=C(C(=O)O)C=CC=1C(CC(=O)C)=O XEWFWIVHLHQTLK-UHFFFAOYSA-N 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 1
- DAFWPLNJBFUCGL-UHFFFAOYSA-N 5-methoxy-4-methyl-2-(3-oxobutanoylamino)benzenesulfonic acid Chemical compound COC1=CC(S(O)(=O)=O)=C(NC(=O)CC(C)=O)C=C1C DAFWPLNJBFUCGL-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-N Acetoacetic acid Natural products CC(=O)CC(O)=O WDJHALXBUFZDSR-UHFFFAOYSA-N 0.000 description 1
- DKQVAQOWUOISMQ-UHFFFAOYSA-N CC(=O)CC(=O)C1=CC(=CC(=C1)S(=O)(=O)O)O Chemical compound CC(=O)CC(=O)C1=CC(=CC(=C1)S(=O)(=O)O)O DKQVAQOWUOISMQ-UHFFFAOYSA-N 0.000 description 1
- ODEARZDPDZDUST-UHFFFAOYSA-N CC1=C(C(=CC=C1)C(=O)O)C(=O)CC(=O)C Chemical class CC1=C(C(=CC=C1)C(=O)O)C(=O)CC(=O)C ODEARZDPDZDUST-UHFFFAOYSA-N 0.000 description 1
- VKLQTKOZPLGWQN-UHFFFAOYSA-N CC1=C(C=C(C=C1)NC(=O)CC(=O)C)C(=O)N Chemical compound CC1=C(C=C(C=C1)NC(=O)CC(=O)C)C(=O)N VKLQTKOZPLGWQN-UHFFFAOYSA-N 0.000 description 1
- DJYCSAWYLHPOJT-UHFFFAOYSA-N CC1=CC(=CC(=C1)S(=O)(=O)O)C(=O)CC(=O)C Chemical compound CC1=CC(=CC(=C1)S(=O)(=O)O)C(=O)CC(=O)C DJYCSAWYLHPOJT-UHFFFAOYSA-N 0.000 description 1
- JBIRFVAAWZBZQF-UHFFFAOYSA-N CCCCCCCCCCCCCCCCNC1=C(C(=CC=C1)OC)C(=O)O Chemical compound CCCCCCCCCCCCCCCCNC1=C(C(=CC=C1)OC)C(=O)O JBIRFVAAWZBZQF-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WFKPHYKFAOXUTI-UHFFFAOYSA-N NP-101A Chemical compound CC(=O)NC1=CC=CC=C1C(N)=O WFKPHYKFAOXUTI-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- QELUYTUMUWHWMC-UHFFFAOYSA-N edaravone Chemical compound O=C1CC(C)=NN1C1=CC=CC=C1 QELUYTUMUWHWMC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- HGVIAKXYAZRSEG-UHFFFAOYSA-N n-(2,4-dimethylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=C(C)C=C1C HGVIAKXYAZRSEG-UHFFFAOYSA-N 0.000 description 1
- KYYRTDXOHQYZPO-UHFFFAOYSA-N n-(2-methoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC=CC=C1NC(=O)CC(C)=O KYYRTDXOHQYZPO-UHFFFAOYSA-N 0.000 description 1
- TVZIWRMELPWPPR-UHFFFAOYSA-N n-(2-methylphenyl)-3-oxobutanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C TVZIWRMELPWPPR-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- BCEOEOBICHVYDJ-UHFFFAOYSA-M sodium;formic acid;formate Chemical compound [Na+].OC=O.[O-]C=O BCEOEOBICHVYDJ-UHFFFAOYSA-M 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Description
本発明は、ジスアゾ顔料組成物の製造方法ならびにジスアゾ顔料組成物を含有してなる印刷インキに関する。 The present invention relates to a method for producing a disazo pigment composition and a printing ink containing the disazo pigment composition.
従来、一般的なプロセス出版のオフセットインキは、顔料の水性ウエットケーキをインキ用ビヒクルないしは溶剤とフラッシングによって相転換を行ってインキ化する方法と、水性ウエットケーキの乾燥物を強力な剪断力によってインキ用ビヒクルに分散することによって得られている。しかし、前者の方法は顔料の水性ウエットケーキ自身の安定性に欠ける性質や、フラッシング性が悪いことによって長時間受ける熱によって不透明化、着色力低下等の品質に対する影響が大きく安定した品質が得られにくかった。 Conventionally, offset ink of general process publishing is a method in which an aqueous wet cake of pigment is converted into an ink by a phase change by an ink vehicle or a solvent and flushing, and a dry product of an aqueous wet cake is printed by a strong shearing force. Obtained by dispersing in a vehicle. However, the former method has a property that the aqueous wet cake of the pigment lacks in stability, and because it has poor flushing properties, it has a large influence on the quality such as opacity and coloring power reduction due to heat received for a long time, and stable quality can be obtained. It was difficult.
そこでこれら品質に対する影響の少ない後者の方法が永続的に継承されているが、水性ウエットケーキ顔料の乾燥物をインキ化したものは乾燥しなかったものからインキ化したものに比較して透明性、流動性、着色力の点で著しく劣っている。ジスアゾ顔料の場合、これら乾燥物からのインキ化物と非乾燥物からのインキ化物の品質の差は、もっぱら乾燥時の熱により著しく結晶が成長してしまうことによって引き起こされている。 Therefore, the latter method, which has little influence on the quality, has been continuously inherited, but the water-based wet cake pigments that have been made into an ink are more transparent than those that have not been dried. It is extremely inferior in terms of fluidity and coloring power. In the case of a disazo pigment, the difference in quality between the ink product from the dried product and the ink product from the non-dried product is caused mainly by crystal growth due to heat during drying.
この結晶成長による品質の低下を解決する手段として二成分の同時カップリングによる解決手段が知られている。たとえば特許文献１ではアセトアセトアニリドとそのフェニル基に極性基を持つものとの混合カップリングする方法が紹介されており、また、特許文献２ではアセトアセトアニリド、アセトアセトオルソアニシジド、アセトアセトオルソトルイジド、アセトアセトオルソクロロアニリド、アセトアセト−２，４−キシリジド、及びアセトアセト−２，５−ジメトキシ−４−クロロアニリドから選ばれる２種類またはそれ以上の混合物をカップリングさせる方法が紹介されているが、いずれの方法も生成したジスアゾ顔料の乾燥物のインキ化物の品質は透明性、流動性、着色力の点でウエットケーキからのインキ化物に対して著しく劣っていた。 As means for solving the deterioration in quality due to crystal growth, a means for solving by simultaneous coupling of two components is known. For example, Patent Document 1 introduces a mixed coupling method between acetoacetanilide and a phenyl group having a polar group, and Patent Document 2 discloses acetoacetanilide, acetoacetoanisidide, and acetoacetoortoluid. A method of coupling two or more mixtures selected from acetoacetoorthochloroanilide, acetoaceto-2,4-xylidide, and acetoaceto-2,5-dimethoxy-4-chloroanilide has been introduced The quality of the ink product of the dried disazo pigment produced by either method was significantly inferior to the ink product from the wet cake in terms of transparency, fluidity and coloring power.
一方、ウエットケーキからのインキ化物の品質向上に対しても永続的に検討がなされており、透明性・流動性を改良する方法として乾燥物からのインキ化同様に、例えば、特許文献３では、ジスアゾ顔料にそれらのスルホン酸化合物を混合する方法が、特許文献４では、カップリング成分としてカルボキシ基および／またはスルホン酸基を有する極性カップリング成分と非極性カップリング成分との混合物を使用して成るジスアゾ顔料を用いる方法が、特許文献５及び特許文献６では、極性カップリング成分と非極性カップリング成分から成る非対称型ジスアゾ化合物を含有するジスアゾ顔料組成物を用いる方法が開示されている。なかでも、特許文献４で開示された製造方法より得られたジスアゾ顔料が印刷インキの透明性を改良する効果が大きいこと、特許文献６で開示されたジスアゾ顔料組成物が印刷インキの流動性を改良する効果が大きいことが開示されており、特許文献７ではアセト酢酸−ｍ−キシリダイド２〜４０モル％、アセト酢酸ｏ−トルイダイド９７．９〜６０モル％、２−アセトアセトアミノ安息香酸０．１〜１０モル％をカップラー成分としてジスアゾ化合物混合物を製造する例が開示されているが、これら使用された極性カップラー成分は水に対して溶解性を示すため、フラッシングが極端に遅くなり結果として長時間の熱履歴によって結晶が成長してしまったり、色相が変化、不透明化したりする事が知られていた。 On the other hand, permanent improvement has also been made to improve the quality of the ink product from the wet cake, and as a method for improving transparency and fluidity, as in the case of inking from the dry product, for example, in Patent Document 3, A method of mixing those sulfonic acid compounds with a disazo pigment is disclosed in Patent Document 4 using a mixture of a polar coupling component having a carboxy group and / or a sulfonic acid group as a coupling component and a nonpolar coupling component. Patent Documents 5 and 6 disclose a method using a disazo pigment comprising a disazo pigment composition containing an asymmetric disazo compound composed of a polar coupling component and a nonpolar coupling component. Among these, the disazo pigment obtained by the production method disclosed in Patent Document 4 has a large effect of improving the transparency of the printing ink, and the disazo pigment composition disclosed in Patent Document 6 exhibits the fluidity of the printing ink. Patent Document 7 discloses that the effect of improvement is great. In Patent Document 7, acetoacetic acid-m-xylidide is 2 to 40 mol%, acetoacetic acid o-toluidide is 97.9 to 60 mol%, 2-acetoacetaminobenzoic acid is 0. Although an example of producing a disazo compound mixture using 1 to 10 mol% as a coupler component is disclosed, since the polar coupler component used is soluble in water, the flushing becomes extremely slow, resulting in a long time. It has been known that crystals grow due to the thermal history of time, and the hue changes and becomes opaque.
また、透明性を改良する方法として、特許文献８には非極性カップリング成分とベンジジン類のテトラゾ成分とのカップリング方法に関して開示されており、極性基を有するカップラー成分を使用することなく透明性を改良する効果が大きいことが報告されているが、先に示した極性カップラー類を一切含んでいないためインキとしての性能は不十分であった。 In addition, as a method for improving transparency, Patent Document 8 discloses a method for coupling a nonpolar coupling component and a tetrazo component of benzidine, so that transparency can be achieved without using a coupler component having a polar group. However, since it does not contain any of the polar couplers shown above, its performance as an ink was insufficient.
また、特許文献９には、特許文献８で示された製造方法を行う際に特許文献５及び特許文献６等で示された極性カップラー成分を併用する方法が開示しているが、顔料と印刷インキ用ビヒクルとのフラッシング直後の透明性は大幅に改良されているものの、着色力が低下する問題は解消していない。 Patent Document 9 discloses a method in which the polar coupler components shown in Patent Document 5 and Patent Document 6 are used in combination when the production method shown in Patent Document 8 is performed. Although the transparency immediately after flushing with the ink vehicle has been greatly improved, the problem of reduced coloring power has not been solved.
透明性や着色力の低下について改良する方法としては、特許文献１０に、バルビツール酸類を用いる方法が記載されている。しかし透明性、着色力の低下は防止されるものの、バルビツール酸類の効果により粒子が微細になりすぎるため静置流動性が劣る問題、色相が非常に赤味によってしまう問題が残っていた。 As a method for improving the decrease in transparency and coloring power, Patent Document 10 describes a method using barbituric acids. However, although the decrease in transparency and coloring power is prevented, the problem that the static fluidity is inferior due to the effect of the barbituric acid and the stationary fluidity is inferior, and the hue is very reddish.
着色力と流動性を同時に改良する方法については、特許文献１１に、ジスアゾ顔料の組成物が開示されている。外層部に特定構造のジスアゾ化合物が局在的に配置されているため高い着色力が得られるものの、逆に透明性については内層側にジスアゾ顔料のみを含有するためカップリング反応中に粒子成長が顕著に発生し、透明性については他の開示されている方法に比べ極めて劣る問題が残っていた。 Regarding a method for simultaneously improving coloring power and fluidity, Patent Document 11 discloses a composition of a disazo pigment. Although a high coloring power can be obtained because the disazo compound having a specific structure is locally arranged in the outer layer portion, conversely, for transparency, only the disazo pigment is contained on the inner layer side, so that particle growth occurs during the coupling reaction. Remarkably occurred, and transparency remained a problem that was extremely inferior to other disclosed methods.
本発明が解決しようとする課題は、オフセットインキ、グラビアインキ等の印刷インキに使用すると、優れた透明性、着色力、流動性を与えるジスアゾ顔料組成物の製造方法を提供することにある。 The problem to be solved by the present invention is to provide a method for producing a disazo pigment composition which, when used in printing inks such as offset inks and gravure inks, provides excellent transparency, coloring power and fluidity.
本発明は、酸性水溶液中にベンジジン類のテトラゾ成分を含むテトラゾ溶液と、数種のカップラー成分を含むカップラー成分とのモル比が１：２〜２．５の比率になるように連続して注入して反応させるジスアゾ顔料組成物の製造方法において、一般式（１）で示されるカップラー成分、バルビツール酸類を必須カップラー成分として構成されるカップラー溶液Ａとテトラゾ成分とをカップリング反応させた後、一般式（１）で示されるカップラー成分、一般式（２）で示されるカップラー成分を必須カップラー成分とするカップラー溶液Ｂとテトラゾ成分とを反応させる事を特徴とするジスアゾ顔料組成物の製造方法に関する。
一般式（１）
ＣＨ3ＣＯＣＨ2ＣＯＮＨ−Ｘ
（式中、Ｘは炭素数１〜４のアルキル基、−ＯＲ基、塩素原子から成る群から選ばれる同一または異なる置換基を有するフェニル基を示す。Ｒは水素原子または炭素数１〜４のアルキル基を表す。）
一般式（２）
ＣＨ3ＣＯＣＨ2ＣＯＮＨ−Ｚ
（式中、Ｚはメチル基、メトキシ基、塩素原子、カルボキシ基もしくはそのアルカリ金属塩、−ＣＯＮＲ2（Ｒ3）基から成る群から選ばれる同一または異なる置換基を有するフェニル基であって、該フェニル基はアセトアセチルアミノ基に対してオルソ位もしくはパラ位のいずれかにカルボキシ基もしくはそのアルカリ金属塩、−ＣＯＮＲ2（Ｒ3）基の少なくとも１種で置換されているフェニル基を有する。ただし、Ｒ2、Ｒ3は互いに独立に、水素原子、炭素数１〜４のアルキル基（該アルキル基は互いに結合して環を形成しても良い。）を表す。）
The present invention continuously injects a molar ratio of a tetrazo solution containing a benzidine tetrazo component and a coupler component containing several types of coupler components in an acidic aqueous solution to a ratio of 1: 2 to 2.5. In the method for producing a disazo pigment composition to be reacted, a coupler component represented by the general formula (1), a coupler solution A composed of barbituric acids as an essential coupler component, and a tetrazo component are subjected to a coupling reaction, The present invention relates to a method for producing a disazo pigment composition comprising reacting a coupler solution represented by the general formula (1) and a coupler solution B containing the coupler component represented by the general formula (2) as an essential coupler component and a tetrazo component. .
General formula (1)
CH 3 COCH 2 CONH-X
(In the formula, X represents a phenyl group having the same or different substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an -OR group, and a chlorine atom. R represents a hydrogen atom or a carbon group having 1 to 4 carbon atoms. Represents an alkyl group.)
General formula (2)
CH 3 COCH 2 CONH-Z
Wherein Z is a phenyl group having the same or different substituent selected from the group consisting of a methyl group, a methoxy group, a chlorine atom, a carboxy group or an alkali metal salt thereof, and a —CONR 2 (R 3 ) group, The phenyl group has a phenyl group substituted with at least one of a carboxy group, an alkali metal salt thereof, and a —CONR 2 (R 3 ) group at either the ortho position or the para position with respect to the acetoacetylamino group. However, R < 2 >, R < 3 > represents a hydrogen atom and a C1-C4 alkyl group mutually independently (this alkyl group may couple | bond together and may form a ring).)
さらに、本発明はカップラー溶液Ａとカップラー溶液Ｂにそれぞれ含まれるカップラー成分のモル比が１：０．２５〜３．０となることを特徴とする上記ジスアゾ顔料組成物の製造方法に関する。 Furthermore, this invention relates to the manufacturing method of the said disazo pigment composition characterized by the molar ratio of the coupler component respectively contained in the coupler solution A and the coupler solution B being 1: 0.25-3.0.
さらに、本発明は上記製造方法にて製造されるジスアゾ顔料組成物に関する。 Furthermore, this invention relates to the disazo pigment composition manufactured with the said manufacturing method.
さらに、本発明はＸ線回折図（ＣｕＫα線）において、ブラッグ角度２θの１０．３〜 １２．０度（２θ）にある最大強度ピークの半価幅が１．３〜１．６度である上記ジスアゾ顔料組成物に関する。 Further, in the present invention, in the X-ray diffraction diagram (CuKα line), the half width of the maximum intensity peak at the Bragg angle 2θ of 10.3 to 12.0 degrees (2θ) is 1.3 to 1.6 degrees. The present invention relates to the disazo pigment composition.
さらに、本発明は２０回繰り返し製造時において、Ｘ線回折図（ＣｕＫα線）ブラッグ角度２θの１０．３〜 １２．０度（２θ）にある最大強度ピークの半価幅の変動係数が、６％以下であることを特徴とする上記ジスアゾ顔料組成物に関する。 Furthermore, in the present invention, the coefficient of variation of the half-value width of the maximum intensity peak at 10.3 to 12.0 degrees (2θ) of the X-ray diffraction diagram (CuKα line) Bragg angle 2θ is 6 at the time of repeated production 20 times. % Of the above-mentioned disazo pigment composition.
さらに、本発明は上記ジスアゾ顔料組成物と印刷インキ用ビヒクルとからなる印刷インキ組成物に関する。 Furthermore, the present invention relates to a printing ink composition comprising the disazo pigment composition and a vehicle for printing ink.
本発明によれば、ジスアゾ顔料組成物の製造方法において、カップラー成分として、カップラー溶液Ａ、カップラー溶液Ｂを用意し、カップラー溶液Ａには一般式（１）、バルビツール酸類を必須構成成分として、カップラー溶液Ｂには一般式（１）、一般式（２）を必須構成成分として、テトラゾ溶液とカップラー溶液して並行して注入するカップリングを行う方法にてジスアゾ顔料組成物を製造することで、色相緑味でありながら着色力が高く、流動性、透明性に優れるジスアゾ顔料組成物が得られる。また本発明によれば、特に印刷インキで重要な透明性に関係する、ジスアゾ顔料組成物のＸ線回折図における半価幅は２０回繰り返し製造時において、きわめて安定しており、繰り返し製造時において高い製造安定性が得られる。 According to the present invention, in the method for producing a disazo pigment composition, a coupler solution A and a coupler solution B are prepared as coupler components, and the coupler solution A has the general formula (1) and barbituric acids as essential components. The coupler solution B has the general formula (1) and the general formula (2) as essential components, and a disazo pigment composition is produced by a method of performing a coupling in which a tetrazo solution and a coupler solution are injected in parallel. A disazo pigment composition having high tinting strength and excellent fluidity and transparency while having a green hue is obtained. Further, according to the present invention, the half-value width in the X-ray diffraction pattern of the disazo pigment composition, which is particularly important for the printing ink, is very stable during repeated production 20 times. High production stability is obtained.
本発明に用いる酸性水溶液は、カップリング反応系を、好ましくはｐＨ３．５〜６．３に保つことができれば良く、従来法のカップリングで使われる公知の酸の水溶液でよい。上記pH領域の保持は、テトラゾの分解や縮合などの副反応を最小化するために必要であり、反応開始から終了時まで上記ｐＨの範囲に維持することが好ましい。このためには、反応途中において酸あるいはアルカリを断続的にあるいは連続的に添加することによっても良いが、操作の容易さの面からはｐＨ緩衝性のある水溶液系、例えば、従来のカップリング反応で良く使われる酢酸−酢酸ナトリウム系やギ酸−ギ酸ナトリウム系等の緩衝性水溶液を用いると、ｐＨの変動が少なく、ｐＨの維持が容易となり好ましいものとなる。 The acidic aqueous solution used in the present invention may be a known acid aqueous solution used in conventional couplings as long as the coupling reaction system can be preferably maintained at pH 3.5 to 6.3. The maintenance of the pH range is necessary to minimize side reactions such as tetrazo decomposition and condensation, and it is preferable to maintain the pH range from the start to the end of the reaction. For this purpose, acid or alkali may be added intermittently or continuously during the reaction. From the viewpoint of ease of operation, an aqueous solution system having pH buffering properties, for example, a conventional coupling reaction may be used. When a buffered aqueous solution such as acetic acid-sodium acetate system or formic acid-sodium formate system, which is often used in (1), is used, there is little fluctuation in pH, and it becomes easy to maintain the pH.
本発明で使用するテトラゾ成分は、３，３’−ジクロロベンジジンや２，２’,５，５’−テトラクロロベンジジンや３，３’−ジメトキシベンジジン、３，３’−ジスルホベンジジン等のベンジジン類を公知の方法でテトラゾ化して得られるものでよく、酸性水溶液として調製する。 The tetrazo component used in the present invention is benzidine such as 3,3′-dichlorobenzidine, 2,2 ′, 5,5′-tetrachlorobenzidine, 3,3′-dimethoxybenzidine, 3,3′-disulfobenzidine, etc. May be obtained by tetrazotization by a known method, and is prepared as an acidic aqueous solution.
本発明で使用されるカップラー溶液としては、カップラー溶液Ａとカップラー溶液Ｂを準備する必要がある。それぞれのカップラー溶液は、カップラー成分がアルカリによって溶解している事が好ましく、数種類のカップラー成分を同時に溶解することが出来る。アルカリとしては、水酸化ナトリウムや水酸化カリウムなどの無機塩基が用いられる。 As a coupler solution used in the present invention, it is necessary to prepare a coupler solution A and a coupler solution B. In each coupler solution, the coupler component is preferably dissolved by alkali, and several types of coupler components can be dissolved simultaneously. As the alkali, an inorganic base such as sodium hydroxide or potassium hydroxide is used.
カップラー溶液Ａには一般式（１）で表されるカップラー成分、バルビツール酸類を必須成分とし、他にカップラーを含んでも良い。バルビツール酸類のモル比率が高すぎると顔料粒子が微細になりすぎて流動性が阻害される事になり、モル比率が低すぎると好ましい透明性が得られない。そのためカップラー溶液Ａにおけるカップラー成分の比率としては、一般式（１）で表されるカップラー成分と、バルビツール酸類のモル比率は１００：０．３〜３．０である事が好ましく、さらには１００：０．５〜２．０である事がさらに好ましい。他にカップラーを含む場合には、一般式（１）で表されるカップラー成分、バルビツール酸類、他に含まれるカップラーとのモル比率は１００：０．５〜２．０：０．１〜１．２である事が好ましく、モル比率に関してバルビツール酸類のモル数が他に含まれるカップラーのモル数より高い事が好ましい。 The coupler solution A contains the coupler component represented by the general formula (1) and barbituric acid as essential components, and may also contain a coupler. If the molar ratio of the barbituric acid is too high, the pigment particles become too fine and the fluidity is hindered. If the molar ratio is too low, preferable transparency cannot be obtained. Therefore, as a ratio of the coupler component in the coupler solution A, the molar ratio of the coupler component represented by the general formula (1) and the barbituric acid is preferably 100: 0.3 to 3.0, more preferably 100 : It is more preferable that it is 0.5-2.0. When other couplers are included, the molar ratio of the coupler component represented by the general formula (1), the barbituric acids, and the other couplers is 100: 0.5 to 2.0: 0.1 to 1. .2 is preferable, and it is preferable that the number of moles of barbituric acid is higher than the number of moles of other couplers contained in terms of mole ratio.
本発明において一般式（１）で表されるカップラー成分としては、アセトアセトアニリド、アセトアセト−ｏ−トルイジド、アセトアセト−ｐ−トルイジド、アセトアセト−ｏ−キシリダイド、アセトアセト−ｍ−キシリダイド、アセトアセト−ｐ−キシリダイド、アセトアセト−ｏ−キシリダイド、アセトアセト−ｏ−メトキシアニリド、アセトアセト−ｍ−メトキシアニリド、アセトアセト−ｐ−メトキシアニリド、アセトアセト−２，３−ジメトキシアニライド、アセトアセト−２，４−ジメトキシアニリド、アセトアセト−２，５−ジメトキシアニリド、アセトアセト−２，６−ジメトキシアニリド、アセトアセト−２，３−ジメトキシ−４−クロロアニリド、アセトアセト−２，３−ジメトキシ−５−クロロアニリド、アセトアセト−２，３−ジメトキシ−６−クロロアニリド、アセトアセト−２，４−ジメトキシ−３−クロロアニリド、アセトアセト−２，４−ジメトキシ−５−クロロアニリド、アセトアセト−２，４−ジメトキシ−６−クロロアニリド、アセトアセト−２，５−ジメトキシ−３−クロロアニリド、アセトアセト−２，５−ジメトキシ−４−クロロアニリド、アセトアセト−２，５−ジメトキシ−６−クロロアニリド、アセトアセト−２，６−ジメトキシ−３−クロロアニリド、アセトアセト−２，６−ジメトキシ−４−クロロアニリド、アセトアセト−２，６−ジメトキシ−５−クロロアニリド、アセトアセト−ｏ−クロロアニリド、アセトアセト−ｍ−クロロアニリド、アセトアセト−ｐ−クロロアニリドなどがあるが、これに限定されるものではない。一般式（１）で表されるものであれば異なる２種類以上の成分を併用してもよい。 As the coupler component represented by the general formula (1) in the present invention, acetoacetanilide, acetoaceto-o-toluidide, acetoaceto-p-toluidide, acetoaceto-o-xylidide, acetoaceto-m-xylide, acetoacet-p-xylide, Acetoaceto-o-xylidide, acetoaceto-o-methoxyanilide, acetoaceto-m-methoxyanilide, acetoaceto-p-methoxyanilide, acetoaceto-2,3-dimethoxyanilide, acetoaceto-2,4-dimethoxyanilide, acetoaceto-2, 5-dimethoxyanilide, acetoaceto-2,6-dimethoxyanilide, acetoaceto-2,3-dimethoxy-4-chloroanilide, acetoaceto-2,3-dimethoxy-5-chloroanilide, acetoacetate -2,3-dimethoxy-6-chloroanilide, acetoaceto-2,4-dimethoxy-3-chloroanilide, acetoaceto-2,4-dimethoxy-5-chloroanilide, acetoaceto-2,4-dimethoxy-6-chloroanilide Acetoaceto-2,5-dimethoxy-3-chloroanilide, acetoaceto-2,5-dimethoxy-4-chloroanilide, acetoaceto-2,5-dimethoxy-6-chloroanilide, acetoaceto-2,6-dimethoxy-3- Chloroanilide, acetoaceto-2,6-dimethoxy-4-chloroanilide, acetoaceto-2,6-dimethoxy-5-chloroanilide, acetoaceto-o-chloroanilide, acetoaceto-m-chloroanilide, acetoaceto-p-chloroanilide, etc. But is limited to this No. As long as it is represented by the general formula (1), two or more different components may be used in combination.
この中でも、アセトアセトアニリド、アセトアセト−ｍ−キシリダイド、アセトアセト−ｏ−トルイジドが本発明においてより効果が発現するため好ましい。 Among these, acetoacetanilide, acetoaceto-m-xylideide, and acetoaceto-o-toluidide are preferable because the effects are more manifested in the present invention.
本発明において、バルビツール酸類とは、バルビツール酸、１，３−ジメチルバルビツール酸、２−チオバルビツール酸、１，３−ジエチル−２−チオ−バルビツール酸、２−イミノ−バルビツール酸、２，４−ジイミノ−バルビツール酸等が挙げられる。好ましくは、バルビツール酸、１，３−ジメチルバルビツール酸が挙げられる。透明性に与える効果の点で、バルビツール酸、１，３−ジメチルバルビツール酸が好ましく、着色力や流動性の改良効果も加味すると、バルビツール酸が最も好ましい。 In the present invention, the barbituric acid refers to barbituric acid, 1,3-dimethylbarbituric acid, 2-thiobarbituric acid, 1,3-diethyl-2-thio-barbituric acid, 2-imino-barbituric And acid, 2,4-diimino-barbituric acid and the like. Preferably, a barbituric acid and 1, 3- dimethyl barbituric acid are mentioned. Barbituric acid and 1,3-dimethylbarbituric acid are preferable in terms of the effect on transparency, and barbituric acid is most preferable in consideration of the effect of improving coloring power and fluidity.
カップラー溶液Ａに一般式（１）、バルビツール酸類の他に含んでもよいカップラーとしては、４−ヒドロキシ−３−アセトアセチルアミノ安息香酸、２−ヒドロキシ−５−アセトアセチルアミノ安息香酸、３−アセトアセチルアミノ−６−メトキシ安息香酸、３−アセトアセチルアミノベンゼンスルホン酸、３−アセトアセチル−５−メチルベンゼンスルホン酸、３−アセトアセチル−５−ヒドロキシ−ベンゼンスルホン酸、４−アセチルアミノ−アセトアセチルアニライド、４−アセトアセチルアミノベンゼンスルホン酸、４−アセトアセチルアミノ−２−メチルベンゼンスルホン酸、２−アセトアセチルアミノ−３−クロロ−４−メチルベンゼンスルホン酸、４−アセトアセチルアミノ−３−メトキシ−２−メチルベンゼンスルホン酸、２−アセトアセチルアミノ−５−メトキシ−４−メチルベンゼンスルホン酸、２−アセトアセチルアミノ−３，５−ジクロロベンゼンスルホン酸、２−アセトアセチルアミノテレフタル酸、２−アセトアセチルアミノフェノール、１−フェニル−３−メチル−５−ピラゾロン等及びこれらのアルカリ金属塩が挙げられるが、これに限られるものではない。 Couplers that may be included in the coupler solution A in addition to the general formula (1) and barbituric acids include 4-hydroxy-3-acetoacetylaminobenzoic acid, 2-hydroxy-5-acetoacetylaminobenzoic acid, 3-acetate Acetylamino-6-methoxybenzoic acid, 3-acetoacetylaminobenzenesulfonic acid, 3-acetoacetyl-5-methylbenzenesulfonic acid, 3-acetoacetyl-5-hydroxy-benzenesulfonic acid, 4-acetylamino-acetoacetyl Anilide, 4-acetoacetylaminobenzenesulfonic acid, 4-acetoacetylamino-2-methylbenzenesulfonic acid, 2-acetoacetylamino-3-chloro-4-methylbenzenesulfonic acid, 4-acetoacetylamino-3- Methoxy-2-methylbenzenesulfonic acid 2-acetoacetylamino-5-methoxy-4-methylbenzenesulfonic acid, 2-acetoacetylamino-3,5-dichlorobenzenesulfonic acid, 2-acetoacetylaminoterephthalic acid, 2-acetoacetylaminophenol, 1-phenyl Examples include, but are not limited to, -3-methyl-5-pyrazolone and alkali metal salts thereof.
カップラー溶液Ｂには、一般式（１）で表されるカップラー成分、一般式（２）で表されるカップラー成分を必須成分とし、他にカップラーを含んでも良い。一般式（２）で表されるカップラー成分は色相緑味を与えるものであり、必要な要求特性に応じて構造を選択することができる。そのためモル比率が低すぎると着色力改良効果、流動性改良効果、色相緑味が得られず、モル比率が高すぎると色相は大きく緑味になるものの生成するジスアゾ化合物がジスアゾ顔料表面に吸着せず、排水負荷が増大する事になる。カップラー溶液Ｂにおけるカップラー成分の比率としては、一般式（１）で表されるカップラー成分と一般式（２）で表されるカップラー成分のモル比率は１００：０．５〜２５．０である事が好ましく、さらには１００：２．０〜２０．０である事がさらに好ましい。他にカップラーを含む場合には、一般式（１）で表されるカップラー成分、一般式（２）で表されるカップラー成分、他に含まれるカップラーとのモル比率は１００：２．０〜２０．０：０．５〜７．０である事が好ましい。 The coupler solution B includes the coupler component represented by the general formula (1) and the coupler component represented by the general formula (2) as essential components, and may also include a coupler. The coupler component represented by the general formula (2) gives hue greenness, and the structure can be selected according to required required characteristics. Therefore, if the molar ratio is too low, the coloring power improving effect, the fluidity improving effect, and the hue greenness cannot be obtained.If the molar ratio is too high, the resulting disazo compound is adsorbed on the surface of the disazo pigment although the hue becomes large and greenish. Therefore, the drainage load will increase. As a ratio of the coupler component in the coupler solution B, the molar ratio of the coupler component represented by the general formula (1) and the coupler component represented by the general formula (2) is 100: 0.5 to 25.0. Is more preferable, and 100: 2.0 to 20.0 is more preferable. When other couplers are included, the molar ratio of the coupler component represented by the general formula (1), the coupler component represented by the general formula (2), and the other couplers is 100: 2.0 to 20 0.0: It is preferable that it is 0.5-7.0.
本発明において、一般式（２）で表されるカップラー成分としては、２−アセトアセチルアミノ安息香酸、４-アセトアセチルアミノ安息香酸、３−ヒドロキシ−４−アセトアセチルアミノ安息香酸、３−ヒドロキシ−４−アセトアセチルアミノ安息香酸、３−メチル−４−アセトアセチル安息香酸、３−メチル−２−アセトアセチル安息香酸、３−クロロ−４−アセトアセチル安息香酸、またはこれらの金属塩、４−アセトアセチルアミノベンズアミド、２−アセトアセチルアミノベンズアミド、Ｎ，Ｎ’−ジメチル−４−アセトアセチルアミノベンズアミド、Ｎ，Ｎ’−ジエチル−４−アセトアセチルアミノベンズアミド、Ｎ，Ｎ’−ジメチルアミノプロピル−４−アセトアセチルベンズアミド、Ｎ，Ｎ’−ジブチルアミノプロピル−４−アセトアセチルベンズアミドなどがあるが、これに限定されるものではなく、一般式（２）で表されるものであれば異なる２種類以上の成分を併用しても良い。 In the present invention, as the coupler component represented by the general formula (2), 2-acetoacetylaminobenzoic acid, 4-acetoacetylaminobenzoic acid, 3-hydroxy-4-acetoacetylaminobenzoic acid, 3-hydroxy- 4-acetoacetylaminobenzoic acid, 3-methyl-4-acetoacetylbenzoic acid, 3-methyl-2-acetoacetylbenzoic acid, 3-chloro-4-acetoacetylbenzoic acid, or a metal salt thereof, 4-acetate Acetylaminobenzamide, 2-acetoacetylaminobenzamide, N, N′-dimethyl-4-acetoacetylaminobenzamide, N, N′-diethyl-4-acetoacetylaminobenzamide, N, N′-dimethylaminopropyl-4- Acetoacetylbenzamide, N, N′-dibutylaminopropyl-4- Although there is acetoacetylbenzamide and the like, it is not limited thereto, and two or more different components may be used in combination as long as they are represented by the general formula (2).
この中でも２−アセトアセチルアミノ安息香酸、４-アセトアセチルアミノ安息香酸、Ｎ，Ｎ’−ジメチル−４−アセトアセチルアミノベンズアミド、４−アセトアセチルアミノベンズアミドが好ましい。一般式（２）で表されるものであれば異なる２種類以上の成分を併用しても良い。 Among these, 2-acetoacetylaminobenzoic acid, 4-acetoacetylaminobenzoic acid, N, N′-dimethyl-4-acetoacetylaminobenzamide, and 4-acetoacetylaminobenzamide are preferable. Two or more different components may be used in combination as long as they are represented by the general formula (2).
カップラー溶液Ｂに一般式（１）、一般式（２）で表されるカップラー成分の他に含まれるカップラーとしては、４−ヒドロキシ−３−アセトアセチルアミノ安息香酸、２−ヒドロキシ−５−アセトアセチルアミノ安息香酸、４−アセチルアミノ−アセトアセチルアニライド、４−アセトアセチルアミノベンゼンスルホン酸、４−アセトアセチルアミノ−２−メチルベンゼンスルホン酸、２−アセトアセチルアミノ−３−クロロ−４−メチルベンゼンスルホン酸、４−アセトアセチルアミノ−３−メトキシ−２−メチルベンゼンスルホン酸、２−アセトアセチルアミノ−５−メトキシ−４−メチルベンゼンスルホン酸、２−アセトアセチルアミノ−３，５−ジクロロベンゼンスルホン酸、２−アセトアセチルアミノテレフタル酸、３−アセトアセチルアミノ−６−メトキシ安息香酸、２−アセトアセチルアミノフェノール、２−メチル−５−アセトアセチルアミノベンズアミド、１−フェニル−３−メチル−５−ピラゾロン等及びこれらのアルカリ金属塩が挙げられるが、これに限られるものではない。 The couplers contained in the coupler solution B in addition to the coupler components represented by the general formulas (1) and (2) include 4-hydroxy-3-acetoacetylaminobenzoic acid and 2-hydroxy-5-acetoacetyl. Aminobenzoic acid, 4-acetylamino-acetoacetylanilide, 4-acetoacetylaminobenzenesulfonic acid, 4-acetoacetylamino-2-methylbenzenesulfonic acid, 2-acetoacetylamino-3-chloro-4-methylbenzene Sulfonic acid, 4-acetoacetylamino-3-methoxy-2-methylbenzenesulfonic acid, 2-acetoacetylamino-5-methoxy-4-methylbenzenesulfonic acid, 2-acetoacetylamino-3,5-dichlorobenzenesulfone Acid, 2-acetoacetylaminoterephthalic acid, 3-aceto Examples include cetylamino-6-methoxybenzoic acid, 2-acetoacetylaminophenol, 2-methyl-5-acetoacetylaminobenzamide, 1-phenyl-3-methyl-5-pyrazolone, and alkali metal salts thereof. It is not limited to.
本発明において、カップラー溶液Ａとカップラー溶液Ｂにそれぞれ含まれるカップラー成分のモル比が１：０．２５〜３．０となることが必要となる。モル比が１：０．２５未満であると、着色力低下、鮮明性の不足を引き起こし、逆に１：３．０より大きいと流動性の低下を引き起こす。 In the present invention, it is necessary that the molar ratio of the coupler component contained in each of the coupler solution A and the coupler solution B is 1: 0.25 to 3.0. When the molar ratio is less than 1: 0.25, the coloring power is lowered and the sharpness is insufficient. On the other hand, when the molar ratio is more than 1: 3.0, the fluidity is lowered.
本発明において、カップラー溶液Ａに含まれるバルビツール酸類のモル比率に対して、カップラー溶液Ｂに含まれるカップラー成分中の一般式（２）で表されるカップラー成分比率の方が高いことが好ましい。これは、最良の着色力、流動性、透明性の改良効果を得るためには、粒子の微細化度に比して一般式（２）で表されるカップラー成分由来のジスアゾ化合物が必要であるためである。またバルビツール酸類により得られる赤味色相を打ち消す上でも、一般式（２）で表されるカップラー成分由来のジスアゾ化合物が多く必要であるためである。 In the present invention, the coupler component ratio represented by the general formula (2) in the coupler component contained in the coupler solution B is preferably higher than the molar ratio of the barbituric acids contained in the coupler solution A. This requires the disazo compound derived from the coupler component represented by the general formula (2) as compared with the fineness of the particles in order to obtain the best effect of improving the coloring power, fluidity and transparency. Because. Moreover, it is because many disazo compounds derived from the coupler component represented by the general formula (2) are necessary for canceling the reddish hue obtained by the barbituric acids.
またカップラー溶液Ａに含まれるバルビツール酸類のモル比率に対して、カップラー溶液Ｂに含まれるカップラー成分中の一般式（２）で表されるカップラー成分比率の方が高いことは、顔料製造工程における反応温度など合成諸条件に対する感度が低くなり、繰り返し製造時において、品質が非常に安定することに寄与する。粒子径の指標であるＸ線回折図における半価幅の平均と標準偏差から求められる変動係数は６％以下となり、従来技術では得ることの出来ない製造安定性が得られる。 Further, the coupler component ratio represented by the general formula (2) in the coupler component contained in the coupler solution B is higher than the molar ratio of barbituric acids contained in the coupler solution A in the pigment production process. Sensitivity to various conditions such as reaction temperature is lowered, which contributes to very stable quality during repeated production. The coefficient of variation obtained from the average and standard deviation of the half width in the X-ray diffraction diagram, which is an index of the particle diameter, is 6% or less, and production stability that cannot be obtained by the prior art is obtained.
本発明の製造方法においてジスアゾ顔料組成物は、酸性水溶液中にカップラー成分とテトラゾ成分とを並行して注入し、酸性水溶液中でカップラー成分とテトラゾ成分とをカップリングさせることにより製造される。 In the production method of the present invention, the disazo pigment composition is produced by injecting a coupler component and a tetrazo component in an acidic aqueous solution in parallel, and coupling the coupler component and the tetrazo component in the acidic aqueous solution.
本発明の製造方法においては、カップラー成分が実質的に析出することがないように、ベンジジン類のテトラゾ溶液とカップラー溶液を同時に並行して注入することが好ましい。（以下並行注入と呼ぶ）。好ましくはすべての時間において並行して注入する事が望ましいが、必要に応じていずれか一方のみが注入される時間があっても良い。カップラー溶液とテトラゾ溶液が直接接触すると、カップラーの析出が起こり固体となるため、カップリング反応が急激に遅延する。そのため本発明の効果は小さくなる場合がある。 In the production method of the present invention, it is preferable to inject a tetrazo solution of benzidine and a coupler solution simultaneously in parallel so that the coupler component does not substantially precipitate. (Hereinafter referred to as parallel injection). Preferably, the injection is performed in parallel at all times, but there may be a time during which only one of them is injected as necessary. When the coupler solution and the tetrazo solution are in direct contact with each other, the coupler is precipitated and becomes a solid, so that the coupling reaction is rapidly delayed. Therefore, the effect of the present invention may be reduced.
これを避けるため、酸性水溶液が満たされた撹拌槽へテトラゾ溶液とカップラー溶液の注入管の出口を互いに離して注入を行いつつ十分に撹拌を行う事で、確実にテトラゾニウム塩とカップラーとが酸性溶液中で反応するようにする事が好ましい。 In order to avoid this, the tetrazonium salt and the coupler are reliably mixed with the acidic solution by thoroughly stirring while injecting the outlets of the tetrazo solution and the coupler solution into the stirring tank filled with the acidic aqueous solution. It is preferable to make it react in.
本発明においては、カップラー溶液Ａとテトラゾ溶液の並行注入をまず行い、カップリング反応によりジスアゾ顔料粒子を形成させる。透明性はカップラー溶液Ａの組成によって決定されるため、特にバルビツール酸類がカップラー溶液Ａ中に均一に溶解していることが必要である。カップラー溶液Ａとテトラゾ溶液のカップリング反応が終了した後に、引き続きカップラー溶液Ｂとテトラゾ溶液との並行注入を行い、カップリング反応を行う。未反応で残っているカップラー析出による反応率低下を防止するためにも前者のカップリング反応終了から後者のカップリング反応が始まるまでの時間は短い方がよく、設備の切り替えにかかる時間など必要最低限の時間以外には、実質的に連続である事が好ましい。 In the present invention, parallel injection of the coupler solution A and the tetrazo solution is first performed, and disazo pigment particles are formed by a coupling reaction. Since the transparency is determined by the composition of the coupler solution A, it is particularly necessary that the barbituric acids are uniformly dissolved in the coupler solution A. After the coupling reaction between the coupler solution A and the tetrazo solution is completed, the coupler solution B and the tetrazo solution are subsequently injected in parallel to perform the coupling reaction. In order to prevent the reaction rate from decreasing due to unreacted remaining coupler precipitation, the time from the end of the former coupling reaction to the start of the latter coupling reaction should be short, and the minimum required time for equipment switching, etc. Except for the limited time, it is preferably substantially continuous.
カップラー溶液Ａとテトラゾ溶液の並行注入、カップラー溶液Ｂとテトラゾ溶液の並行注入におけるテトラゾ成分とカップラー成分の総量のモル比率は１：２〜１：２．５である必要がある。比率が１：２以下ではテトラゾ成分過剰になり色相が汚れ、１：２．５より大きい場合、未反応カップラーが顔料粒子に取り込まれ品質低下を引き起こす。 The molar ratio of the total amount of the tetrazo component and the coupler component in the parallel injection of the coupler solution A and the tetrazo solution and the parallel injection of the coupler solution B and the tetrazo solution needs to be 1: 2 to 1: 2.5. When the ratio is 1: 2 or less, the tetrazo component becomes excessive and the hue becomes dirty. When the ratio is greater than 1: 2.5, unreacted couplers are incorporated into the pigment particles and cause a reduction in quality.
供給するモル速度は一定である必要はなく、カップラー成分とテトラゾ成分のモル比率は上記比率の範囲内で変化させても良い。またカップラー溶液の注入を先行させても良い。さらに界面活性剤やロジンなどを同時に注入し顔料粒子の表面処理を同時に行う事も出来る。 It is not necessary for the molar rate to be supplied to be constant, and the molar ratio of the coupler component and the tetrazo component may be changed within the above range. Moreover, the injection of the coupler solution may be preceded. Furthermore, the surface treatment of the pigment particles can be simultaneously performed by simultaneously injecting a surfactant or rosin.
本発明においてジスアゾ顔料の顔料特性を向上させるために、ジスアゾ顔料の水スラリーに対して硫酸アルミニウム、塩化アルミニウムおよび塩化カルシウムからなる群から選ばれる水溶性無機塩を添加すること、あるいはロジン類あるいは印刷インキ用ビヒクルまたはその金属塩によって顔料の表面処理を施してもよい。表面処理用のロジンの種類としては、ガムロジン、ウッドロジン、トール油ロジン、不均化ロジン、重合ロジン、水添ロジン、マレイン化ロジン等の顔料のロジン処理に一般的に使用されるロジンの水酸化ナトリウム溶液もしくは水酸化カリウム溶液などがある。表面処理用の印刷インキ用ビヒクルとしては、酸価が高くアルカリ水溶液となるロジン変性フェノール樹脂が好ましく、これにアルキッド樹脂、石油樹脂等を併用しても良い。ロジンまたは印刷インキ用ビヒクルの添加量は、固形分換算でカップリングして生成されるジスアゾ顔料に対して、２〜１５０重量％、好ましくは３〜８０重量％である。 In order to improve the pigment properties of the disazo pigment in the present invention, a water-soluble inorganic salt selected from the group consisting of aluminum sulfate, aluminum chloride and calcium chloride is added to the water slurry of the disazo pigment, or rosins or printing The pigment may be surface treated with an ink vehicle or a metal salt thereof. Types of rosin for surface treatment include rosin hydroxylation generally used for rosin treatment of pigments such as gum rosin, wood rosin, tall oil rosin, disproportionated rosin, polymerized rosin, hydrogenated rosin and maleated rosin. Examples include sodium solution or potassium hydroxide solution. As the vehicle for printing ink for surface treatment, a rosin-modified phenol resin having a high acid value and an alkaline aqueous solution is preferable, and an alkyd resin, petroleum resin or the like may be used in combination. The amount of the rosin or printing ink vehicle added is 2 to 150% by weight, preferably 3 to 80% by weight, based on the disazo pigment produced by coupling in terms of solid content.
本発明の製造法によって得られたジスアゾ顔料組成物は、Ｘ線回折図（ＣｕＫα線）において、ブラッグ角度２θの１０．３〜１２．０度にある最大ピークの半価幅が１．３〜１．６度であることを特徴とする。Ｘ線回折図における半価幅はインキにした場合の透明性に良く相関しており、１．３度を下回る顔料である場合は透明性が不足し、１．６度を超える場合は、分散不良を起こすことからやはり透明性が不足することになる。 The disazo pigment composition obtained by the production method of the present invention has a full width at half maximum of 1.3 to 12.0 degrees at a Bragg angle 2θ of 1.3 to 12.0 in an X-ray diffraction diagram (CuKα ray). It is characterized by 1.6 degrees. The half-value width in the X-ray diffraction diagram correlates well with the transparency when made into ink, and when the pigment is less than 1.3 degrees, the transparency is insufficient, and when it exceeds 1.6 degrees, the dispersion Transparency is still lacking because it causes defects.
本発明の製造法によって得られたジスアゾ顔料組成物は繰り返し製造時において、品質が非常に安定することを特徴とする。粒子径の指標であるＸ線回折図における半価幅の平均と標準偏差から求められる変動係数は６％以下となり、従来技術では得ることの出来ない製造安定性である。 The disazo pigment composition obtained by the production method of the present invention is characterized in that the quality is very stable during repeated production. The coefficient of variation obtained from the average and standard deviation of the half-value width in the X-ray diffraction diagram, which is an index of the particle diameter, is 6% or less, which is a production stability that cannot be obtained by the prior art.
本発明の製造法によって得られたジスアゾ顔料組成物は、印刷インキ用ビヒクルと混練されて、透明性と流動性に優れた印刷インキに使用することができる。オフセットインキ用ビヒクルとしては、例えば、ロジン変成フェノール樹脂、石油樹脂、アルキッド樹脂またはこれら乾性油変成樹脂等の樹脂と、必要に応じて、アマニ油、桐油、大豆油等の植物油と、ｎ−パラフィン、イソパラフィン、アロマテック、ナフテン、α−オレフィン等の溶剤から成るものであって、それらの混合割合は、重量比で樹脂：植物油：溶剤＝２０〜５０部：０〜３０部：１０〜６０部の範囲が好ましい。本発明のジスアゾ顔料を配合したオフセットインキ用ビヒクルは、必要に応じて、インキ溶剤、ドライヤー、レベリング改良剤、増粘剤等の公知の添加剤を適宜配合して印刷インキとすることができる。 The disazo pigment composition obtained by the production method of the present invention can be kneaded with a printing ink vehicle and used for printing inks having excellent transparency and fluidity. Vehicles for offset ink include, for example, rosin modified phenolic resin, petroleum resin, alkyd resin, or resins such as these dry oil modified resins, and vegetable oils such as linseed oil, tung oil, soybean oil, and n-paraffin, if necessary. , Isoparaffin, aroma tech, naphthene, α-olefin and the like, and the mixing ratio thereof is resin: vegetable oil: solvent = 20-50 parts: 0-30 parts: 10-60 parts by weight. The range of is preferable. The offset ink vehicle in which the disazo pigment of the present invention is blended can be made into a printing ink by appropriately blending known additives such as an ink solvent, a drier, a leveling improver, and a thickener, if necessary.
以下に実施例によって本発明を更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、以下の例中「部」及び「％」は、特に断りのない限りいずれも「重量部」、「重量％」を示す。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In the following examples, “parts” and “%” indicate “parts by weight” and “% by weight” unless otherwise specified.
＜実施例１＞
３，３’−ジクロロベンジジン塩酸塩を４倍モルの塩酸と、２倍モルの亜硝酸ナトリウムを用いてテトラゾ化し、０．３００ｍｏｌ／Ｌのテトラゾ溶液を得た。別の容器にカップラーＡ液として水５９２ｇに対しアセトアセトアニライド７３．４９ｇ、バルビツール酸０．８１ｇ、水酸化ナトリウム２４ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。別の容器にカップラーＢ液として、水１３３３ｇに対し、アセトアセトアニライド１３７．２８ｇ、２−アセトアセチルアミノ安息香酸７．９９ｇ、４−アセトアセチルアミノベンズアミド７．９５ｇ、水酸化ナトリウム４８ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。
<Example 1>
3,3′-Dichlorobenzidine hydrochloride was tetrazotized using 4 times mol of hydrochloric acid and 2 times mol of sodium nitrite to obtain a 0.300 mol / L tetrazo solution. In a separate container, 73.49 g of acetoacetanilide, 0.81 g of barbituric acid, and 24 g of sodium hydroxide were added to 592 g of water as Coupler A solution, and stirred until the coupler was dissolved and cleared. In a separate container, as a coupler B solution, 137.28 g of acetoacetanilide, 7.99 g of 2-acetoacetylaminobenzoic acid, 7.95 g of 4-acetoacetylaminobenzamide, and 48 g of sodium hydroxide are added to 1333 g of water. Stir until the coupler is dissolved and clear.
さらに反応缶に、８０％酢酸１０４ｇ、水酸化ナトリウム２８ｇ、水２０００ｇを投入し十分に攪拌した。 Further, 104 g of 80% acetic acid, 28 g of sodium hydroxide, and 2000 g of water were added to the reaction vessel and sufficiently stirred.
反応缶に対し、テトラゾ溶液の連続滴下を開始し、カップラー溶液Ａが４０分で滴下が終了するよう、Ｈ酸のチェックで過剰のテトラゾが存在しないようテトラゾ溶液と同時に注入開始した。カップラー溶液Ａの注入が終了した後、速やかにカップラー溶液Ｂに切り替え、さらに８０分でカップラー溶液Ｂの注入が終わるように注入を行った。反応の際、Ｈ酸によるチェックにて、過剰のテトラゾ液が存在していなかった。さらにテトラゾ溶液を注入し、テトラゾ溶液がわずかに過剰になるまで注入し、１０分間撹拌し反応を完結させた。 Continuous dripping of the tetrazo solution was started to the reaction can, and injection was started simultaneously with the tetrazo solution so that excessive tetrazo was not present by checking the H acid so that the dripping of the coupler solution A was completed in 40 minutes. After the injection of the coupler solution A was completed, it was quickly switched to the coupler solution B, and the injection was performed so that the injection of the coupler solution B was completed in 80 minutes. During the reaction, an excess of tetrazo liquid was not present by checking with H acid. Further, a tetrazo solution was injected, and the solution was injected until the tetrazo solution became slightly excessive, and stirred for 10 minutes to complete the reaction.
上記反応液をｐＨ１２．０に調整し、６０℃まで加熱撹拌した後、不均化ロジンを固形分で１８．８ｇ投入し、塩酸でｐＨを８．５に調整した後、硫酸アルミニウム６．３ｇを添加し、塩酸にてｐＨを５．５に調整し顔料スラリーを得た。このスラリーのろ過を行い、十分に水洗を行った後、顔料ウエットケーキを得た。 The reaction solution was adjusted to pH 12.0 and heated and stirred to 60 ° C., then 18.8 g of disproportionated rosin was added as a solid content, pH was adjusted to 8.5 with hydrochloric acid, and then 6.3 g of aluminum sulfate was added. And the pH was adjusted to 5.5 with hydrochloric acid to obtain a pigment slurry. The slurry was filtered and sufficiently washed with water, to obtain a pigment wet cake.
＜比較例１＞
実施例１のカップラー溶液Ａとカップラー溶液Ｂを混ぜ合わせカップラー溶液とし、その溶液が１２０分で滴下が終了するよう滴下した以外は、実施例１と同様にして顔料ウエットケーキを得た。
<Comparative Example 1>
A pigment wet cake was obtained in the same manner as in Example 1 except that the coupler solution A and the coupler solution B of Example 1 were mixed to form a coupler solution, and the solution was added dropwise so that the addition was completed in 120 minutes.
＜実施例２＞
３，３’−ジクロロベンジジン塩酸塩を４倍モルの塩酸と、２倍モルの亜硝酸ナトリウムを用いてテトラゾ化し、０．３００ｍｏｌ／Ｌのテトラゾ溶液を得た。別の容器にカップラーＡ液として水１６００ｇに対しアセトアセトアニライド１７６．９２ｇ、バルビツール酸１．５５ｇ、水酸化ナトリウム５７．６ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。別の容器にカップラーＢ液として、水４００ｇに対し、アセトアセトアニライド４１．１９ｇ、２−アセトアセチルアミノ安息香酸２．２４ｇ、４−アセトアセチルアミノベンズアミド２．２３ｇ、水酸化ナトリウム１４．４ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。
<Example 2>
3,3′-Dichlorobenzidine hydrochloride was tetrazotized using 4 times mol of hydrochloric acid and 2 times mol of sodium nitrite to obtain a 0.300 mol / L tetrazo solution. In a separate container, 176.92 g of acetoacetanilide, 1.55 g of barbituric acid, and 57.6 g of sodium hydroxide were added to 1600 g of water as Coupler A solution, and stirred until the coupler was dissolved and cleared. In a separate container, as a coupler B solution, 41.19 g of acetoacetanilide, 2.24 g of 2-acetoacetylaminobenzoic acid, 2.23 g of 4-acetoacetylaminobenzamide, and 14.4 g of sodium hydroxide are added to 400 g of water. Stir until the coupler is dissolved and clear.
さらに反応缶に、８０％酢酸１０４ｇ、水酸化ナトリウム２８ｇ、水２０００ｇを投入し十分に攪拌した。 Further, 104 g of 80% acetic acid, 28 g of sodium hydroxide, and 2000 g of water were added to the reaction vessel and sufficiently stirred.
反応缶に対し、テトラゾ溶液の連続滴下を開始し、カップラー溶液Ａが９６分で滴下が終了するよう、Ｈ酸のチェックで過剰のテトラゾが存在しないようテトラゾ溶液と同時に注入開始した。カップラー溶液Ａの注入が終了した後、速やかにカップラー溶液Ｂに切り替え、さらに２４分でカップラー溶液Ｂの注入が終わるように注入を行った。反応の際、Ｈ酸によるチェックにて、過剰のテトラゾ液が存在していなかった。さらにテトラゾ溶液を注入し、テトラゾ溶液がわずかに過剰になるまで注入し、１０分間撹拌し反応を完結させた。 Continuous dripping of the tetrazo solution was started to the reaction can, and injection was started simultaneously with the tetrazo solution so that excessive tetrazo was not present in the H acid check so that the dropping of the coupler solution A was completed in 96 minutes. After the injection of the coupler solution A was completed, it was quickly switched to the coupler solution B, and the injection was performed so that the injection of the coupler solution B was completed in 24 minutes. During the reaction, an excess of tetrazo liquid was not present by checking with H acid. Further, a tetrazo solution was injected, and the solution was injected until the tetrazo solution became slightly excessive, and stirred for 10 minutes to complete the reaction.
上記反応液をｐＨ１０．０に調整し、６０℃まで加熱撹拌した後、不均化ロジンを固形分で１８．８ｇ投入し、塩酸でｐＨを６．５に調整した後、硫酸アルミニウム６．３ｇを添加し１０分間撹拌を行って、顔料スラリーを得た。このスラリーのろ過を行い、十分に水洗を行った後、顔料ウエットケーキを得た。 The reaction solution was adjusted to pH 10.0 and heated and stirred to 60 ° C., then 18.8 g of disproportionated rosin was added as a solid content, the pH was adjusted to 6.5 with hydrochloric acid, and then 6.3 g of aluminum sulfate. Was added and stirred for 10 minutes to obtain a pigment slurry. The slurry was filtered and sufficiently washed with water, to obtain a pigment wet cake.
＜実施例３＞
３，３’−ジクロロベンジジン塩酸塩を４倍モルの塩酸と、２倍モルの亜硝酸ナトリウムを用いてテトラゾ化し、０．３００ｍｏｌ／Ｌのテトラゾ溶液を得た。別の容器にカップラーＡ液として水８００ｇに対しアセトアセトアニライド８７．７４ｇ、４−ヒドロキシ−３−アセトアセチルアミノ安息香酸０．６ｇ、バルビツール酸０．９７ｇ、水酸化ナトリウム２８．８ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。別の容器にカップラーＢ液として、水１２００ｇに対し、アセトアセトアニライド１２３．５６ｇ、４−ヒドロキシ−３−アセトアセチルアミノ安息香酸５．３９ｇ、２−アセトアセチルアミノ安息香酸５．０３ｇ、４−アセトアセチルアミノベンズアミド３．３４ｇ、水酸化ナトリウム４３．２ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。
<Example 3>
3,3′-Dichlorobenzidine hydrochloride was tetrazotized using 4 times mol of hydrochloric acid and 2 times mol of sodium nitrite to obtain a 0.300 mol / L tetrazo solution. In another container, 87.74 g of acetoacetanilide, 0.6 g of 4-hydroxy-3-acetoacetylaminobenzoic acid, 0.97 g of barbituric acid, and 28.8 g of sodium hydroxide are added to 800 g of water as Coupler A solution. And stirred until the coupler was dissolved and cleared. As a Coupler B solution in another container, 123.56 g of acetoacetanilide, 5.39 g of 4-hydroxy-3-acetoacetylaminobenzoic acid, 5.03 g of 2-acetoacetylaminobenzoic acid, Acetoacetylaminobenzamide (3.34 g) and sodium hydroxide (43.2 g) were added and stirred until the coupler was dissolved and cleared.
さらに反応缶に、８０％酢酸１０４ｇ、水酸化ナトリウム２８ｇ、水２０００ｇを投入し十分に攪拌した。 Further, 104 g of 80% acetic acid, 28 g of sodium hydroxide, and 2000 g of water were added to the reaction vessel and sufficiently stirred.
反応缶に対し、テトラゾ溶液の連続滴下を開始し、カップラー溶液Ａが４０分で滴下が終了するよう、Ｈ酸のチェックで過剰のテトラゾが存在しないようテトラゾ溶液と同時に注入開始した。カップラー溶液Ａの注入が終了した後、速やかにカップラー溶液Ｂに切り替え、さらに８０分でカップラー溶液Ｂの注入が終わるように注入を行った。反応の際、Ｈ酸によるチェックにて、過剰のテトラゾ液が存在していなかった。さらにテトラゾ溶液を注入し、テトラゾ溶液がわずかに過剰になるまで注入し、１０分間撹拌し反応を完結させた。 Continuous dripping of the tetrazo solution was started to the reaction can, and injection was started simultaneously with the tetrazo solution so that excessive tetrazo was not present by checking the H acid so that the dripping of the coupler solution A was completed in 40 minutes. After the injection of the coupler solution A was completed, it was quickly switched to the coupler solution B, and the injection was performed so that the injection of the coupler solution B was completed in 80 minutes. During the reaction, an excess of tetrazo liquid was not present by checking with H acid. Further, a tetrazo solution was injected, and the solution was injected until the tetrazo solution became slightly excessive, and stirred for 10 minutes to complete the reaction.
上記反応液をｐＨ１２．０に調整し、６０℃まで加熱撹拌した後、不均化ロジンを固形分で１８．８ｇ投入し、塩酸でｐＨを８．５に調整した後、硫酸アルミニウム６．３ｇを添加し、塩酸にてｐＨを５．５に調整し顔料スラリーを得た。このスラリーのろ過を行い、十分に水洗を行った後、顔料ウエットケーキを得た。 The reaction solution was adjusted to pH 12.0 and heated and stirred to 60 ° C., then 18.8 g of disproportionated rosin was added as a solid content, pH was adjusted to 8.5 with hydrochloric acid, and then 6.3 g of aluminum sulfate was added. And the pH was adjusted to 5.5 with hydrochloric acid to obtain a pigment slurry. The slurry was filtered and sufficiently washed with water, to obtain a pigment wet cake.
＜比較例２＞
３，３’−ジクロロベンジジン塩酸塩を４倍モルの塩酸と、２倍モルの亜硝酸ナトリウムを用いてテトラゾ化し、０．３００ｍｏｌ／Ｌのテトラゾ溶液を得た。別の容器にカップラーＡ液として水８００ｇに対しアセトアセトアニライド８９．５３ｇ、水酸化ナトリウム２８．８ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。別の容器にカップラーＢ液として、水１２００ｇに対し、アセトアセトアニライド１２１．７７ｇ、４−ヒドロキシ−３−アセトアセチルアミノ安息香酸５．９９ｇ、２−アセトアセチルアミノ安息香酸５．０３ｇ、４−アセトアセチルアミノベンズアミド３．３４ｇ、バルビツール酸０．９７ｇ、水酸化ナトリウム４３．２ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。
<Comparative example 2>
3,3′-Dichlorobenzidine hydrochloride was tetrazotized using 4 times mol of hydrochloric acid and 2 times mol of sodium nitrite to obtain a 0.300 mol / L tetrazo solution. In a separate container, 89.53 g of acetoacetanilide and 28.8 g of sodium hydroxide were added to 800 g of water as Coupler A solution, and stirred until the coupler was dissolved and cleared. As a Coupler B solution in another container, 121.77 g of acetoacetanilide, 5.99 g of 4-hydroxy-3-acetoacetylaminobenzoic acid, 5.03 g of 2-acetoacetylaminobenzoic acid, 4-200 g of water, Acetoacetylaminobenzamide (3.34 g), barbituric acid (0.97 g), and sodium hydroxide (43.2 g) were added and stirred until the coupler was dissolved and cleared.
さらに反応缶に、８０％酢酸１０４ｇ、水酸化ナトリウム２８ｇ、水２０００ｇを投入し十分に攪拌した。 Further, 104 g of 80% acetic acid, 28 g of sodium hydroxide, and 2000 g of water were added to the reaction vessel and sufficiently stirred.
反応缶に対し、テトラゾ溶液の連続滴下を開始し、カップラー溶液Ａが４８分で滴下が終了するよう、Ｈ酸のチェックで過剰のテトラゾが存在しないようテトラゾ溶液と同時に注入開始した。カップラー溶液Ａの注入が終了した後、速やかにカップラー溶液Ｂに切り替え、さらに７２分でカップラー溶液Ｂの注入が終わるように注入を行った。反応の際、Ｈ酸によるチェックにて、過剰のテトラゾ液が存在していなかった。さらにテトラゾ溶液を注入し、テトラゾ溶液がわずかに過剰になるまで注入し、１０分間撹拌し反応を完結させた。 Continuous dripping of the tetrazo solution was started to the reaction can, and injection was started simultaneously with the tetrazo solution so that excessive tetrazo was not present in the H acid check so that the dripping of the coupler solution A was completed in 48 minutes. After the injection of the coupler solution A was completed, it was quickly switched to the coupler solution B, and the injection was performed so that the injection of the coupler solution B was completed in 72 minutes. During the reaction, an excess of tetrazo liquid was not present by checking with H acid. Further, a tetrazo solution was injected, and the solution was injected until the tetrazo solution became slightly excessive, and stirred for 10 minutes to complete the reaction.
上記反応液をｐＨ１２．０に調整し、６０℃まで加熱撹拌した後、不均化ロジンを固形分で１８．８ｇ投入し、塩酸でｐＨを８．５に調整した後、硫酸アルミニウム６．３ｇを添加し、塩酸にてｐＨを５．５に調整し顔料スラリーを得た。このスラリーのろ過を行い、十分に水洗を行った後、顔料ウエットケーキを得た。 The reaction solution was adjusted to pH 12.0 and heated and stirred to 60 ° C., then 18.8 g of disproportionated rosin was added as a solid content, pH was adjusted to 8.5 with hydrochloric acid, and then 6.3 g of aluminum sulfate was added. And the pH was adjusted to 5.5 with hydrochloric acid to obtain a pigment slurry. The slurry was filtered and sufficiently washed with water, to obtain a pigment wet cake.
＜比較例３＞
３，３’−ジクロロベンジジン塩酸塩を４倍モルの塩酸と、２倍モルの亜硝酸ナトリウムを用いてテトラゾ化し、０．３００ｍｏｌ／Ｌのテトラゾ溶液を得た。別ウエットケーキラーＡ液として水８００ｇに対しアセトアセトアニライド８９．５３ｇ、水酸化ナトリウム２８．８ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。別の容器にカップラーＢ液として、水１２００ｇに対し、アセトアセトアニライド１２３．５６ｇ、４−ヒドロキシ−３−アセトアセチルアミノ安息香酸５．３９ｇ、２−アセトアセチルアミノ安息香酸５．０３ｇ、４−アセトアセチルアミノベンズアミド３．３４ｇ、水酸化ナトリウム４３．２ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。
<Comparative Example 3>
3,3′-Dichlorobenzidine hydrochloride was tetrazotized using 4 times mol of hydrochloric acid and 2 times mol of sodium nitrite to obtain a 0.300 mol / L tetrazo solution. As another wet cake liquor A, 89.53 g of acetoacetanilide and 28.8 g of sodium hydroxide were added to 800 g of water, and stirred until the coupler was dissolved and cleared. As a Coupler B solution in another container, 123.56 g of acetoacetanilide, 5.39 g of 4-hydroxy-3-acetoacetylaminobenzoic acid, 5.03 g of 2-acetoacetylaminobenzoic acid, Acetoacetylaminobenzamide (3.34 g) and sodium hydroxide (43.2 g) were added and stirred until the coupler was dissolved and cleared.
さらに反応缶に、８０％酢酸１０４ｇ、水酸化ナトリウム２８ｇ、水２０００ｇを投入し十分に攪拌した。 Further, 104 g of 80% acetic acid, 28 g of sodium hydroxide, and 2000 g of water were added to the reaction vessel and sufficiently stirred.
反応缶に対し、テトラゾ溶液の連続滴下を開始し、カップラー溶液Ａが４８分で滴下が終了するよう、Ｈ酸のチェックで過剰のテトラゾが存在しないようテトラゾ溶液と同時に注入開始した。カップラー溶液Ａの注入が終了した後、速やかにカップラー溶液Ｂに切り替え、さらに７２分でカップラー溶液Ｂの注入が終わるように注入を行った。反応の際、Ｈ酸によるチェックにて、過剰のテトラゾ液が存在していなかった。さらにテトラゾ溶液を注入し、テトラゾ溶液がわずかに過剰になるまで注入し、１０分間撹拌し反応を完結させた。 Continuous dripping of the tetrazo solution was started to the reaction can, and injection was started simultaneously with the tetrazo solution so that excessive tetrazo was not present in the H acid check so that the dripping of the coupler solution A was completed in 48 minutes. After the injection of the coupler solution A was completed, it was quickly switched to the coupler solution B, and the injection was performed so that the injection of the coupler solution B was completed in 72 minutes. During the reaction, an excess of tetrazo liquid was not present by checking with H acid. Further, a tetrazo solution was injected, and the solution was injected until the tetrazo solution became slightly excessive, and stirred for 10 minutes to complete the reaction.
上記反応液をｐＨ１２．０に調整し、６０℃まで加熱撹拌した後、不均化ロジンを固形分で１８．８ｇ投入し、塩酸でｐＨを８．５に調整した後、硫酸アルミニウム６．３ｇを添加し、塩酸にてｐＨを５．５に調整し顔料スラリーを得た。このスラリーのろ過を行い、十分に水洗を行った後、顔料ウエットケーキを得た。 The reaction solution was adjusted to pH 12.0 and heated and stirred to 60 ° C., then 18.8 g of disproportionated rosin was added as a solid content, pH was adjusted to 8.5 with hydrochloric acid, and then 6.3 g of aluminum sulfate was added. And the pH was adjusted to 5.5 with hydrochloric acid to obtain a pigment slurry. The slurry was filtered and sufficiently washed with water, to obtain a pigment wet cake.
＜実施例４〜９＞
３，３’−ジクロロベンジジン塩酸塩を４倍モルの塩酸と、２倍モルの亜硝酸ナトリウムを用いてテトラゾ化し、０．３００ｍｏｌ／Ｌのテトラゾ溶液を得た。表１、表２にしたがってカップラー溶液Ａ、カップラー溶液Ｂを用意し、表の滴下時間に従ってカップリング反応を行い、反応液を得た。
<Examples 4 to 9>
3,3′-Dichlorobenzidine hydrochloride was tetrazotized using 4 times mol of hydrochloric acid and 2 times mol of sodium nitrite to obtain a 0.300 mol / L tetrazo solution. A coupler solution A and a coupler solution B were prepared according to Tables 1 and 2, and a coupling reaction was performed according to the dropping time in the table to obtain a reaction solution.
得られた反応液それぞれに対しをｐＨ１２．０に調整し、６０℃まで加熱撹拌した後、不均化ロジンを固形分で１８．８ｇ投入し、塩酸でｐＨを８．５に調整した後、硫酸アルミニウム６．３ｇを添加し、塩酸にてｐＨを５．５に調整し顔料スラリーをそれぞれ得た。このスラリーのろ過を行い、十分に水洗を行った後、顔料ウエットケーキをそれぞれ得た。 Each of the obtained reaction liquids was adjusted to pH 12.0 and heated and stirred to 60 ° C., then 18.8 g of disproportionated rosin was added as a solid content, and the pH was adjusted to 8.5 with hydrochloric acid. 6.3 g of aluminum sulfate was added and the pH was adjusted to 5.5 with hydrochloric acid to obtain pigment slurries. The slurry was filtered and sufficiently washed with water, and then a pigment wet cake was obtained.
＜実施例１０＞
３，３’−ジクロロベンジジン塩酸塩を４倍モルの塩酸と、２倍モルの亜硝酸ナトリウムを用いてテトラゾ化し、０．３００ｍｏｌ／Ｌのテトラゾ溶液を得た。別の容器にカップラーＡ液として水６６７ｇに対しアセトアセトメタキシリダイド８５．５６ｇ、バルビツール酸０．５４ｇ、水酸化ナトリウム２４．０ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。別の容器にカップラーＢ液として、水１３３３ｇに対し、アセトアセトメタキシリダイド１６４．２０ｇ、２−アセトアセチルアミノ安息香酸５．５９ｇ、４−アセトアセチルアミノベンズアミド３．７１ｇ、水酸化ナトリウム４８．０ｇを投入し、カップラーが溶解してクリアになるまで撹拌した。
<Example 10>
3,3′-Dichlorobenzidine hydrochloride was tetrazotized using 4 times mol of hydrochloric acid and 2 times mol of sodium nitrite to obtain a 0.300 mol / L tetrazo solution. In a separate container, 85.56 g of acetoacetmetaxylide, 0.54 g of barbituric acid, and 24.0 g of sodium hydroxide were added to 667 g of water as coupler A solution, and stirred until the coupler was dissolved and cleared. In a separate container, as Coupler B liquid, 1334 g of water, 164.20 g of acetoacetmetaxylide, 5.59 g of 2-acetoacetylaminobenzoic acid, 3.71 g of 4-acetoacetylaminobenzamide, 48.0 g of sodium hydroxide And stirred until the coupler was dissolved and cleared.
さらに反応缶に、８０％酢酸１０４ｇ、水酸化ナトリウム２８ｇ、水２０００ｇを投入し十分に攪拌した。 Further, 104 g of 80% acetic acid, 28 g of sodium hydroxide, and 2000 g of water were added to the reaction vessel and sufficiently stirred.
反応缶に対し、テトラゾ溶液の連続滴下を開始し、カップラー溶液Ａが４０分で滴下が終了するよう、Ｈ酸のチェックで過剰のテトラゾが存在しないようテトラゾ溶液と同時に注入開始した。カップラー溶液Ａの注入が終了した後、速やかにカップラー溶液Ｂに切り替え、さらに８０分でカップラー溶液Ｂの注入が終わるように注入を行った。反応の際、Ｈ酸によるチェックにて、過剰のテトラゾ液が存在していなかった。さらにテトラゾ溶液を注入し、テトラゾ溶液がわずかに過剰になるまで注入し、１０分間撹拌し反応を完結させた。 Continuous dripping of the tetrazo solution was started to the reaction can, and injection was started simultaneously with the tetrazo solution so that excessive tetrazo was not present by checking the H acid so that the dripping of the coupler solution A was completed in 40 minutes. After the injection of the coupler solution A was completed, it was quickly switched to the coupler solution B, and the injection was performed so that the injection of the coupler solution B was completed in 80 minutes. During the reaction, an excess of tetrazo liquid was not present by checking with H acid. Further, a tetrazo solution was injected, and the solution was injected until the tetrazo solution became slightly excessive, and stirred for 10 minutes to complete the reaction.
上記反応液をｐＨ１２．０に調整し、６０℃まで加熱撹拌した後、不均化ロジンを固形分で１８．８ｇ投入し、塩酸でｐＨを８．５に調整した後、硫酸アルミニウム６．３ｇを添加し、塩酸にてｐＨを５．５に調整し顔料スラリーを得た。このスラリーのろ過を行い、十分に水洗を行った後、顔料ウエットケーキを得た。 The reaction solution was adjusted to pH 12.0 and heated and stirred to 60 ° C., then 18.8 g of disproportionated rosin was added as a solid content, pH was adjusted to 8.5 with hydrochloric acid, and then 6.3 g of aluminum sulfate was added. And the pH was adjusted to 5.5 with hydrochloric acid to obtain a pigment slurry. The slurry was filtered and sufficiently washed with water, to obtain a pigment wet cake.
＜比較例４＞
実施例１のカップラー溶液Ａとカップラー溶液Ｂを混ぜ合わせカップラー溶液とし、その溶液が１２０分で滴下が終了するよう滴下した以外は、実施例１０と同様にして顔料ウエットケーキを得た。
<Comparative example 4>
A pigment wet cake was obtained in the same manner as in Example 10 except that the coupler solution A and the coupler solution B of Example 1 were mixed to form a coupler solution, and the solution was added dropwise so that the addition was completed in 120 minutes.
＜実施例１１＞
実施例１０のカップラー溶液Ａのアセトアセトメタキシリダイド８５．５６ｇをアセトアセトオルソトルイジド７９．７１ｇ、カップラー溶液Ｂのアセトアセトメタキシリダイド１６４．２０ｇをアセトアセトオルソトルイジド１５２．９８ｇとしたほかは、実施例１０と同様にして顔料ウエットケーキを得た。
<Example 11>
85.56 g of acetoacetometaxylide in coupler solution A of Example 10 was 79.71 g of acetoacetoortho toluidide, and 164.20 g of acetoacetometaxylide in coupler solution B was 152.98 g of acetoacetoortholide. A pigment wet cake was obtained in the same manner as in Example 10.
＜比較例５＞
実施例１１のカップラー溶液Ａとカップラー溶液Ｂを混ぜ合わせカップラー溶液とし、その溶液が１２０分で滴下が終了するよう滴下した以外は、実施例１１と同様にして顔料ウエットケーキを得た。
<Comparative Example 5>
A pigment wet cake was obtained in the same manner as in Example 11 except that the coupler solution A and the coupler solution B of Example 11 were mixed to form a coupler solution, and the solution was added dropwise so that the addition was completed in 120 minutes.
＜実施例１２＞
実施例１０のカップラー溶液Ａのアセトアセトメタキシリダイド８５．５６ｇをアセトアセトオルソアニシジド８５．９５ｇ、カップラー溶液Ｂのアセトアセトメタキシリダイド１６４．２０ｇをアセトアセトオルソアニシジド１６５．７８ｇとしたほかは、実施例１０と同様にして顔料ウエットケーキを得た。
<Example 12>
In addition to 85.56 g of acetoacetometaxidide in coupler solution A of Example 10 being 85.95 g of acetoacetometaxanidide and 164.20 g of acetoacetometaxylide in coupler solution B being 165.78 g of acetoacetosoanisidide. Produced a pigment wet cake in the same manner as in Example 10.
＜比較例６＞
実施例１２のカップラー溶液Ａとカップラー溶液Ｂを混ぜ合わせカップラー溶液とし、その溶液が１２０分で滴下が終了するよう滴下した以外は、実施例１２と同様にして顔料ウエットケーキを得た。
<Comparative Example 6>
A pigment wet cake was obtained in the same manner as in Example 12 except that the coupler solution A and the coupler solution B of Example 12 were mixed to form a coupler solution, and the solution was added dropwise so that the addition was completed in 120 minutes.
＜実施例１３＞
実施例１０のカップラー溶液Ａのアセトアセトメタキシリダイド８５．５６ｇをアセトアセト−５−ジメトキシ−４−クロロアニライド１１３．２６ｇ、カップラー溶液Ｂのアセトアセトメタキシリダイド１６４．２０ｇをアセトアセト−２、５−ジメトキシ−４−クロロアニライド２１７．３６ｇとしたほかは、実施例１０と同様にして顔料ウエットケーキを得た。
<Example 13>
85.56 g of acetoacetmetaxylide in coupler solution A of Example 10 was 113.26 g of acetoacet-5-dimethoxy-4-chloroanilide, and 164.20 g of acetoacetmetaxylide in coupler solution B was acetoacetate-2, 5 A pigment wet cake was obtained in the same manner as in Example 10 except that 217.36 g of -dimethoxy-4-chloroanilide was used.
＜比較例７＞
実施例１３のカップラー溶液Ａとカップラー溶液Ｂを混ぜ合わせカップラー溶液とし、その溶液が１２０分で滴下が終了するよう滴下した以外は、実施例１１と同様にして顔料ウエットケーキを得た。
<Comparative Example 7>
A pigment wet cake was obtained in the same manner as in Example 11 except that the coupler solution A and coupler solution B of Example 13 were mixed to form a coupler solution, and the solution was added dropwise so that the addition was completed in 120 minutes.
＜実施例１４＞
実施例１０のカップラー溶液Ａのアセトアセトメタキシリダイド８５．５６ｇ、バルビツール酸０．５４ｇ、をアセトアセトメタキシリダイド５０．８２ｇ、アセトアセトオルソトルイジド４７．３４ｇ、バルビツール酸１．０８ｇとし、カップラー溶液Ｂのアセトアセトメタキシリダイド１６４．２０ｇをアセトアセトメタキシリダイド７３．８９ｇ、アセトアセトオルソトルイジド６８．８４ｇとしたほかは、実施例１０と同様にして顔料ウエットケーキを得た。
<Example 14>
85.56 g of acetoacetmetaxylide of coupler solution A of Example 10 and 0.54 g of barbituric acid, 50.82 g of acetoacetometaxylide, 47.34 g of acetoacetoortholuidide, 1.08 g of barbituric acid A pigment wet cake was obtained in the same manner as in Example 10 except that 164.20 g of acetoacetmetaxylide in coupler solution B was changed to 73.89 g of acetoacetmetaxylide and 68.84 g of acetoacetoortholide. It was.
＜比較例８＞
実施例１４のカップラー溶液Ａとカップラー溶液Ｂを混ぜ合わせカップラー溶液とし、その溶液が１２０分で滴下が終了するよう滴下した以外は、実施例１１と同様にして顔料ウエットケーキを得た。
<Comparative Example 8>
A pigment wet cake was obtained in the same manner as in Example 11 except that the coupler solution A and the coupler solution B of Example 14 were mixed to form a coupler solution, and the solution was added dropwise so that the addition was completed in 120 minutes.
実施例の条件をまとめると表１のようになる。なお、表１の中で(a)〜(m)で表されるカップラーは表２のとおりである。 Table 1 summarizes the conditions of the example. In Table 1, the couplers represented by (a) to (m) are as shown in Table 2.
表１
表２
＜顔料ウエットケーキのＸ線回折測定＞
上記実施例もしくは比較例で得られた顔料ウエットケーキに対し、Ｘ 線回折測定において、１０．３〜 １２．０度（２θ）にある最大強度ピークの半価幅の測定を行い、顔料粒子径の測定方法とした。
Ｘ 線回折スペクトルは下記条件で測定を実施した。表３に測定結果を示した。
装置： ＲＩＧＡＫＵ Ｕｌｔｉｍａ２００１
Ｘ線源： ＣｕＫα
電圧： ４０ｋＶ
電流： ４０ｍＡ
測定範囲： ５．０° から３５．０°
ステップ角： ０．０２°
<X-ray diffraction measurement of pigment wet cake>
The half-width of the maximum intensity peak at 10.3 to 12.0 degrees (2θ) was measured in the X-ray diffraction measurement for the pigment wet cake obtained in the above examples or comparative examples, and the pigment particle diameter The measurement method was as follows.
The X-ray diffraction spectrum was measured under the following conditions. Table 3 shows the measurement results.
Device: RIGAKU Ultimate 2001
X-ray source: CuKα
Voltage: 40kV
Current: 40 mA
Measurement range: 5.0 ° to 35.0 °
Step angle: 0.02 °
表３
＜実施例１５＞
オフセットインキ化方法
フラッシングによるインキ化は１Ｌフラッシャーを用いて行った。すなわち実施例１で得られた顔料ウエットケーキを乾燥重量で８０部と、予め１００℃に温めたオフセットインキ用ビヒクル１９０部をフラッシャー中に同時に投入し、フラッシングを行った（オープンフラッシング工程：トータル時間１５分）。次にフラッシングで出てきた水を除去後、減圧（１〜８×１０3 Ｐａ）及びインキ内の温度が１００℃になるまで加熱を６０分間行いインキ中の水を完全に除去した（バキュームフラッシング工程）。このインキにオフセットインキ用ビヒクル３９０部と溶剤４４部を徐々に加えたのちフラッシャーから取り出した。その後、３本ロールを用いてロール温度６０℃、１０Ｂａｒｒの圧力をかけて練肉し粗大粒子を除去し、ベースインキを得た。このベースインキ６２部にオフセットインキ用ビヒクル２５部、溶剤１０部、補助剤３部加えタック５．８〜６．０に調整して最終インキを得た。
<Example 15>
Ink-inking method Inking by flushing was performed using a 1 L flasher. That is, 80 parts by weight of the pigment wet cake obtained in Example 1 and 190 parts of an offset ink vehicle preliminarily warmed to 100 ° C. were simultaneously charged into the flasher and flushed (open flushing process: total time 15 minutes). Next, after removing the water that came out by flushing, heating was performed for 60 minutes until the temperature in the ink reached 100 ° C. under reduced pressure (1 to 8 × 10 3 Pa), and water in the ink was completely removed (vacuum flushing). Process). To this ink, 390 parts of an offset ink vehicle and 44 parts of solvent were gradually added and then taken out from the flasher. Then, using 3 rolls, a roll temperature of 60 ° C. and a pressure of 10 Barr was applied to knead and remove coarse particles to obtain a base ink. The final ink was obtained by adding 25 parts of the vehicle for offset ink, 10 parts of the solvent and 3 parts of the auxiliary agent to 62 parts of the base ink and adjusting the tack to 5.8 to 6.0.
＜実施例１６〜２８、比較例９〜１６＞
実施例１で得られた顔料ウエットケーキを、実施例２〜１４および比較例１〜８で得られた顔料ウエットケーキにそれぞれ置き換えた以外は、実施例１５と同様にして最終インキを得た。
<Examples 16 to 28, Comparative Examples 9 to 16>
A final ink was obtained in the same manner as in Example 15 except that the pigment wet cake obtained in Example 1 was replaced with the pigment wet cake obtained in Examples 2 to 14 and Comparative Examples 1 to 8, respectively.
＜インキ評価＞
得られた各最終インキについて、色相、着色力、光沢、流動性を測定した。測定した結果は表４に示す。着色力は、得られたインキをオフ輪インキ用の展色紙に対してＪＩＳ Ｋ ５７０１−１によって定められた展色方法に則ってインキ０．１５ｇを展色し、常法により乾燥して展色物を得た。
<Ink evaluation>
Each final ink obtained was measured for hue, tinting strength, gloss, and fluidity. The measured results are shown in Table 4. The coloring power is obtained by developing 0.15 g of ink on the developed paper for off-ring ink according to the color development method defined by JIS K 5701-1, and drying it by a conventional method. A colored product was obtained.
この展色物の反射率濃度を調べ、比較例１２は実施例２４で得られた着色力を１００としたとき、比較例１３は実施例２５で得られた着色力を１００としたとき、比較例１４は実施例２６で得られた着色力を１００としたとき、比較例１５は実施例２７で得られた着色力を１００としたとき、比較例１６は実施例２８で得られた着色力を１００としたときの数値を示した。色相に関しては、得られた展色物を測色し、比較例１２〜１６をそれぞれ基準としてΔａ＊の数字が大きければ赤味、小さければ緑味を示す。 The reflectance density of this color-extended product was examined. Comparative Example 12 was compared when the coloring power obtained in Example 24 was 100, and Comparative Example 13 was compared when the coloring power obtained in Example 25 was 100. In Example 14, when the coloring power obtained in Example 26 was set to 100, in Comparative Example 15, the coloring power obtained in Example 27 was set to 100, and in Comparative Example 16, the coloring power obtained in Example 28 was used. The numerical value is shown when 100 is 100. With respect to the hue, the obtained color-extracted object is measured, and if the number of Δa * is large with Comparative Examples 12 to 16 as a reference, it shows reddish, and if it is small, it shows greenish.
流動性に関しては、傾斜版のインキ壺に各最終インキを入れ、１時間静置した後に、９０°に傾け、３０分間流動した長さ（静置したインキの下端から下方に向かって流動したインキの先端までの長さ）をｍｍ単位で測定した。透明性に関しては、１０段階で評価した。黒帯のある展色紙に対して展色したうえで、黒帯上の透過具合を見て判断した。 Regarding the fluidity, each final ink was put into an inclined ink fountain and allowed to stand for 1 hour, then tilted to 90 °, and allowed to flow for 30 minutes (ink that flowed downward from the lower end of the stationary ink) Was measured in mm. The transparency was evaluated in 10 stages. Judgment was made by looking at the degree of transparency on the black belt after developing the color on the black colored belt.
表４
表４から明らかなように、従来技術である比較例９〜１６においては、色相緑味、着色力、流動性、透明性すべてを併せ持つ顔料組成物を製造することは難しかったが、本発明の技術を用いることで、従来技術では難しいとされていた色相緑味と高着色力、透明性、高い流動性を併せ持つ顔料組成物が製造できることがわかる。 As is clear from Table 4, in Comparative Examples 9 to 16, which are conventional techniques, it was difficult to produce a pigment composition having all of hue greenness, coloring power, fluidity, and transparency. It can be seen that by using this technique, it is possible to produce a pigment composition having both hue greenness, high coloring power, transparency and high fluidity, which has been considered difficult in the prior art.
＜実施例２９＞
実施例１について、２０回繰り返し製造を行い、それぞれ顔料ウエットケーキを得た。得られた顔料ウエットケーキに対し、Ｘ 線回折測定において、１０．３〜 １２．０度（２θ）にある最大強度ピークの半価幅の測定を行った。それぞれ測定した結果をまとめると半価幅の平均値１．５５０、標準偏差０．０６５６、変動係数４．２３％となった。
<Example 29>
About Example 1, it manufactured repeatedly 20 times and obtained the pigment wet cake, respectively. The half-width of the maximum intensity peak at 10.3 to 12.0 degrees (2θ) was measured for the obtained pigment wet cake in X-ray diffraction measurement. When the measured results were summarized, the average value of the half width was 1.550, the standard deviation was 0.0656, and the coefficient of variation was 4.23%.
＜実施例３０＞
実施例３について、２０回繰り返し製造を行い、それぞれ顔料ウエットケーキを得た。得られた顔料ウエットケーキに対し、Ｘ 線回折測定において、１０．３〜 １２．０度（２θ）にある最大強度ピークの半価幅の測定を行った。それぞれ測定した結果をまとめると半価幅の平均値１．４５４、標準偏差０．０７８７、変動係数５．４１％となった。
<Example 30>
About Example 3, it manufactured repeatedly 20 times and obtained the pigment wet cake, respectively. The half-width of the maximum intensity peak at 10.3 to 12.0 degrees (2θ) was measured for the obtained pigment wet cake in X-ray diffraction measurement. When the results of measurement were summarized, the average value of the full width at half maximum was 1.454, the standard deviation was 0.0787, and the coefficient of variation was 5.41%.
＜比較例１７＞
比較例１について、２０回繰り返し製造を行い、それぞれ顔料ウエットケーキを得た。得られた顔料ウエットケーキに対し、Ｘ 線回折測定において、１０．３〜 １２．０度（２θ）にある最大強度ピークの半価幅の測定を行った。それぞれ測定した結果をまとめると半価幅の平均値１．０８２、標準偏差０．０８４１、変動係数７．７６％となった。
<Comparative Example 17>
About the comparative example 1, it manufactured repeatedly 20 times and obtained the pigment wet cake, respectively. The half-width of the maximum intensity peak at 10.3 to 12.0 degrees (2θ) was measured for the obtained pigment wet cake in X-ray diffraction measurement. When the measurement results were summarized, the average value of the half width was 1.082, the standard deviation was 0.0841, and the coefficient of variation was 7.76%.
＜比較例１８＞
比較例３について、２０回繰り返し製造を行い、それぞれ顔料ウエットケーキを得た。得られた顔料ウエットケーキに対し、Ｘ 線回折測定において、１０．３〜 １２．０度（２θ）にある最大強度ピークの半価幅の測定を行った。それぞれ測定した結果をまとめると半価幅の平均値０．８５５、標準偏差０．０９８０、変動係数１１．２％となった。
<Comparative Example 18>
About the comparative example 3, it manufactured repeatedly 20 times and obtained the pigment wet cake, respectively. The half-width of the maximum intensity peak at 10.3 to 12.0 degrees (2θ) was measured for the obtained pigment wet cake in X-ray diffraction measurement. When the measurement results are summarized, the average half-value width is 0.855, the standard deviation is 0.0980, and the coefficient of variation is 11.2%.
実施例２９、３０、および、比較例１７、１８の結果から明らかなように、本発明の技術を用いることで、従来技術では難しいとされてきた高い製造安定性が得られた。
As is clear from the results of Examples 29 and 30 and Comparative Examples 17 and 18, by using the technique of the present invention, high production stability, which has been considered difficult by the prior art, was obtained.
Claims (6)
一般式（１）
ＣＨ3ＣＯＣＨ2ＣＯＮＨ−Ｘ
（式中、Ｘは炭素数１〜４のアルキル基、−ＯＲ基、塩素原子から成る群から選ばれる同一または異なる置換基を有するフェニル基を示す。Ｒは水素原子または炭素数１〜４のアルキル基を表す。）
一般式（２）
ＣＨ3ＣＯＣＨ2ＣＯＮＨ−Ｚ
（式中、Ｚはメチル基、メトキシ基、塩素原子、カルボキシ基もしくはそのアルカリ金属塩、−ＣＯＮＲ2（Ｒ3）基から成る群から選ばれる同一または異なる置換基を有するフェニル基であって、該フェニル基はアセトアセチルアミノ基に対してオルソ位もしくはパラ位のいずれかにカルボキシ基もしくはそのアルカリ金属塩、−ＣＯＮＲ2（Ｒ3）基の少なくとも１種で置換されているフェニル基を有する。ただし、Ｒ2Ｒ3は互いに独立に、水素原子、炭素数１〜４のアルキル基（該アルキル基は互いに結合して環を形成しても良い。）を表す。） The reaction is carried out by continuously injecting the reaction so that the molar ratio of the tetrazo solution containing the benzidine tetrazo component to the coupler component containing several types of coupler components in the acidic aqueous solution is 1: 2 to 2.5. In the method for producing a disazo pigment composition, a coupling reaction between a coupler component A represented by the general formula (1) and a barbituric acid as an essential coupler component and a tetrazo solution is performed, and then the general formula (1 ) And a coupler solution B having a coupler component represented by the general formula (2) as an essential coupler component and a tetrazo solution are reacted with each other, thereby producing a disazo pigment composition.
General formula (1)
CH 3 COCH 2 CONH-X
(In the formula, X represents a phenyl group having the same or different substituents selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an -OR group, and a chlorine atom. R represents a hydrogen atom or a carbon group having 1 to 4 carbon atoms. Represents an alkyl group.)
General formula (2)
CH 3 COCH 2 CONH-Z
Wherein Z is a phenyl group having the same or different substituent selected from the group consisting of a methyl group, a methoxy group, a chlorine atom, a carboxy group or an alkali metal salt thereof, and a —CONR 2 (R 3 ) group, The phenyl group has a phenyl group substituted with at least one of a carboxy group, an alkali metal salt thereof, and a —CONR 2 (R 3 ) group at either the ortho position or the para position with respect to the acetoacetylamino group. R 2 R 3 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (the alkyl groups may be bonded to each other to form a ring).
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