JP4687186B2 - Dioxazine violet pigment composition - Google Patents
Dioxazine violet pigment composition Download PDFInfo
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- JP4687186B2 JP4687186B2 JP2005094467A JP2005094467A JP4687186B2 JP 4687186 B2 JP4687186 B2 JP 4687186B2 JP 2005094467 A JP2005094467 A JP 2005094467A JP 2005094467 A JP2005094467 A JP 2005094467A JP 4687186 B2 JP4687186 B2 JP 4687186B2
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- dioxazine violet
- pigment composition
- violet pigment
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- 239000000049 pigment Substances 0.000 title claims description 130
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 title claims description 87
- 239000000203 mixture Substances 0.000 title claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 22
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical class ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 claims description 20
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000011164 primary particle Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims description 2
- HDECRAPHCDXMIJ-UHFFFAOYSA-N 2-methylbenzenesulfonyl chloride Chemical compound CC1=CC=CC=C1S(Cl)(=O)=O HDECRAPHCDXMIJ-UHFFFAOYSA-N 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical class ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000976 ink Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 22
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 22
- 238000007639 printing Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000000020 Nitrocellulose Substances 0.000 description 10
- 229920001220 nitrocellulos Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 10
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 239000003973 paint Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003849 aromatic solvent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HFFXLYHRNRKAPM-UHFFFAOYSA-N 2,4,5-trichloro-n-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C(=CC(Cl)=C(Cl)C=2)Cl)=N1 HFFXLYHRNRKAPM-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009837 dry grinding Methods 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 229920006284 nylon film Polymers 0.000 description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 2
- 230000019612 pigmentation Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- IQOJIHIRSVQTJJ-UHFFFAOYSA-N 3-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(Cl)=C1 IQOJIHIRSVQTJJ-UHFFFAOYSA-N 0.000 description 1
- MWWNNNAOGWPTQY-UHFFFAOYSA-N 3-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=CC(S(Cl)(=O)=O)=C1 MWWNNNAOGWPTQY-UHFFFAOYSA-N 0.000 description 1
- ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 4-chlorobenzenesulfonyl chloride Chemical compound ClC1=CC=C(S(Cl)(=O)=O)C=C1 ZLYBFBAHAQEEQQ-UHFFFAOYSA-N 0.000 description 1
- JXRGUPLJCCDGKG-UHFFFAOYSA-N 4-nitrobenzenesulfonyl chloride Chemical compound [O-][N+](=O)C1=CC=C(S(Cl)(=O)=O)C=C1 JXRGUPLJCCDGKG-UHFFFAOYSA-N 0.000 description 1
- OXEUETBFKVCRNP-UHFFFAOYSA-N 9-ethyl-3-carbazolamine Chemical compound NC1=CC=C2N(CC)C3=CC=CC=C3C2=C1 OXEUETBFKVCRNP-UHFFFAOYSA-N 0.000 description 1
- ONMOULMPIIOVTQ-UHFFFAOYSA-N 98-47-5 Chemical compound OS(=O)(=O)C1=CC=CC([N+]([O-])=O)=C1 ONMOULMPIIOVTQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OIFVNPXDPQOQIL-UHFFFAOYSA-N O1ON=CC=C1.[Na] Chemical compound O1ON=CC=C1.[Na] OIFVNPXDPQOQIL-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- MZZSDCJQCLYLLL-UHFFFAOYSA-N Secalonsaeure A Natural products COC(=O)C12OC3C(CC1=C(O)CC(C)C2O)C(=CC=C3c4ccc(O)c5C(=O)C6=C(O)CC(C)C(O)C6(Oc45)C(=O)OC)O MZZSDCJQCLYLLL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004985 dialkyl amino alkyl group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000485 pigmenting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Description
本発明は、顔料として印刷インキ、塗料、着色成形品、捺染の用途に用いることの出来るジオキサジンバイオレット顔料組成物に関するものであり、さらに詳しくは、グラビア印刷インキやフレキソ印刷インキの用途において、特に光沢に優れた特性を示すジオキサジンバイオレット顔料組成物に関する。 The present invention relates to a dioxazine violet pigment composition that can be used as a pigment in printing inks, paints, colored molded articles, and textile printing applications, and more particularly in gravure printing inks and flexographic printing inks. The present invention relates to a dioxazine violet pigment composition exhibiting excellent gloss properties.
ジオキサジンバイオレット顔料の平版印刷インキ、グラビア印刷インキ、フレキソ印刷インキ又は塗料用途での光沢及び／又は流動性向上には、ジオキサジンバイオレット顔料の誘導体が使用されている。この様な、ジオキサジンバイオレット顔料の誘導体としては、例えば、それに対応するスルホン酸誘導体、スルホンアミド誘導体、ジアルキルアミノアルキル誘導体、フタルイミドアルキル誘導体等が知られている。 Dioxazine violet pigment derivatives are used to improve gloss and / or fluidity in lithographic printing inks, gravure printing inks, flexographic printing inks or paint applications of dioxazine violet pigments. As such derivatives of dioxazine violet pigment, for example, sulfonic acid derivatives, sulfonamide derivatives, dialkylaminoalkyl derivatives, phthalimidoalkyl derivatives and the like corresponding thereto are known.
ジオキサジンバイレット顔料とジオキサジンバイレット顔料の誘導体とを含む顔料組成物の製造方法としては、例えば、ジオキサジンバイオレット粗顔料を食塩のような磨砕助剤とポリエチレングリコールのような湿潤剤を併用してニーダー、バンバリーミキサー等によって磨砕する、ソルベントソルトミリング法による顔料化方法や、ジオキサジンバイオレット粗顔料をボールミル、アトライター、または振動ボールミル等で乾式磨砕して、乾式磨砕物とした後に、アルコール類と水の混合溶媒、ケトン類と水の混合溶媒、または芳香族溶媒と水の混合溶媒と共にソルベントボイリング処理する顔料化方法等によって、予めジオキサジンバイオレット顔料だけを製造しておき、その後に、これと対応するジオキサジンバイオレット顔料の誘導体とを混合して顔料組成物する方法がある。 As a method for producing a pigment composition containing a dioxazine billet pigment and a derivative of a dioxazine billet pigment, for example, a dioxazine violet crude pigment is mixed with a grinding aid such as sodium chloride and a wetting agent such as polyethylene glycol. Combined grinding with a kneader, Banbury mixer, etc., pigmentation method by solvent salt milling method, dioxazine violet crude pigment is dry-milled with a ball mill, attritor, vibration ball mill, etc. to make a dry milled product Later, only dioxazine violet pigment is produced in advance by a pigmentation method or the like in which solvent boiling treatment is performed together with a mixed solvent of alcohols and water, a mixed solvent of ketones and water, or a mixed solvent of aromatic solvent and water, After that, the corresponding dioxazine violet pigment A method of pigment composition by mixing a body.
また、３−アミノ−９−エチルカルバゾールとクロラニルの縮合・閉環によってジオキサジンバイオレット粗顔料を製造する段階で、上記した様なジオキサジンバイオレット顔料の誘導体を併用して、ジオキサジンバイオレット顔料の誘導体を含有するジオキサジンバイオレット粗顔料を製造した後、上記した様な公知の方法でその粗顔料組成物を顔料化する方法が提案されている。 In addition, in the step of producing a dioxazine violet crude pigment by condensation / ring-closing of 3-amino-9-ethylcarbazole and chloranil, a dioxazine violet pigment derivative as described above is used in combination with the dioxazine violet pigment derivative as described above. There has been proposed a method of producing a crude dioxazine violet crude pigment and then pigmenting the crude pigment composition by a known method as described above.
しかしながら、前記した従来のジオキサジンバイオレット顔料の誘導体を併用する方法は、それを含有する着色皮膜の光沢低下が現れるという欠点があった。しかも、ジオキサジンバイオレット顔料の誘導体を含有する顔料組成物は親水性となり、耐ブリード性に劣る（ブリードとは、着色皮膜の耐水性が劣り、水分が付着した場合に色素が溶け出す性質）欠点がある上に使用する用途によっては、増粘（粘度上昇）による流動性低下等の欠点が現れる場合があった。 However, the above-described conventional method of using a dioxazine violet pigment derivative has a drawback in that the gloss of the colored film containing it appears to be lowered. Moreover, the pigment composition containing the derivative of dioxazine violet pigment becomes hydrophilic and has poor bleeding resistance (bleed is the property that the coloring film has poor water resistance and the property that the dye dissolves when moisture adheres). In addition, depending on the application used, there are cases where defects such as a decrease in fluidity due to thickening (increased viscosity) may appear.
特許文献１には、ジオキサジンバイオレットの粗顔料を製造する段階で、上記ジオキサジンバイオレット顔料のスルホン酸誘導体等を併用して、ジオキサジンバイオレット顔料のスルホン酸誘導体等を含有するジオキサジンバイオレット粗顔料を製造し、この粗顔料を常法により顔料化する方法が提案されている。
また特許文献２には、ジオキサジンバイオレット顔料のウエットケーキにジオキサジンバイオレット色素のスルホンアミド系誘導体を加えて、サンドミルで湿式粉砕した後、常法により濾過、水洗、乾燥してスルホンアミド系誘導体を含有するジオキサジンバイオレット顔料を製造する方法が提案されている。
特許文献３には、ジオキサジンバイオレット顔料に対して、比較的多量のベンゼンスルホン酸誘導体を加えて粉砕し、それを水酸化カリウム水溶液に加えてスラリーとして高温で攪拌後、濾過水洗乾燥するジオキサジンバイレット顔料の製造方法が記載されている。
Patent Document 1 discloses a dioxazine violet crude pigment containing a sulfonic acid derivative of a dioxazine violet pigment in combination with the sulfonic acid derivative of the dioxazine violet pigment at the stage of producing a crude dioxazine violet pigment. Has been proposed, and this crude pigment is converted into a pigment by a conventional method.
In Patent Document 2, a sulfonamide derivative of dioxazine violet dye is added to a wet cake of dioxazine violet pigment, wet pulverized with a sand mill, filtered, washed with water and dried to obtain a sulfonamide derivative. A method for producing the contained dioxazine violet pigment has been proposed.
Patent Document 3 discloses a dioxazine that is pulverized by adding a relatively large amount of a benzenesulfonic acid derivative to a dioxazine violet pigment, added to an aqueous potassium hydroxide solution, stirred as a slurry at high temperature, washed with filtered water, and dried. A method for producing a billet pigment is described.
特許文献１〜３の方法から得られたジオキサジンバイオレット顔料組成物は、いずれも、それから着色皮膜を形成した場合に光沢が低いという欠点があった。また、ジオキサジンバイオレット顔料の誘導体を含有する顔料組成物は、いずれも親水性となり、例えば、耐ブリード性に劣ったり、使用する用途によっては流動性不良（粘度上昇）等の欠点が現れる場合があった。 Each of the dioxazine violet pigment compositions obtained from the methods of Patent Documents 1 to 3 has a drawback that the gloss is low when a colored film is formed therefrom. In addition, any pigment composition containing a derivative of dioxazine violet pigment becomes hydrophilic, for example, it may be inferior in bleed resistance, or may exhibit defects such as poor fluidity (increased viscosity) depending on the intended use. there were.
本発明者らは、上記欠点を解決するために、例えば、印刷インキや塗料等において着色皮膜を形成した際の光沢に優れるジオキサジンバイオレット顔料組成物を見出すべく鋭意検討した結果、本発明を完成するに至った。 In order to solve the above-mentioned drawbacks, the present inventors have intensively studied to find a dioxazine violet pigment composition having excellent gloss when a colored film is formed in, for example, printing ink or paint, and as a result, completed the present invention. It came to do.
即ち本発明は、質量基準でジオキサジンバイオレット顔料（Ａ）１００部当たり、ベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体（Ｂ）０．０５〜５．０部を含有する、乾燥したジオキサジンバイオレット顔料組成物を提供する。 That is, the present invention provides a dried dioxazine violet containing 0.05 to 5.0 parts of benzenesulfonic acid derivative and / or benzenesulfonyl chloride derivative (B) per 100 parts of dioxazine violet pigment (A) on a mass basis. A pigment composition is provided.
本発明のジオキサジンバイオレット顔料組成物は、ジオキサジンバイオレット顔料に対してより少量のベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体を含有するので、印刷インキや塗料等において着色皮膜を形成した際の光沢に優れるという格別顕著な効果を奏する。しかも、ジオキサジンバイオレット顔料の誘導体を併用することに共通する耐ブリード性低下の欠点も無く、使用する用途によって問題視される流動性不良（粘度上昇）といった欠点もない。 Since the dioxazine violet pigment composition of the present invention contains a smaller amount of a benzenesulfonic acid derivative and / or a benzenesulfonyl chloride derivative with respect to the dioxazine violet pigment, when a colored film is formed in a printing ink or paint, etc. It has a particularly remarkable effect of being excellent in gloss. In addition, there is no disadvantage of bleed resistance common to the combined use of a dioxazine violet pigment derivative, and there is no disadvantage of poor fluidity (increased viscosity), which is a problem depending on the intended use.
以下、本発明を詳細に説明する。
本発明は、質量基準でジオキサジンバイオレット顔料（Ａ）１００部当たり、ベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体（Ｂ）０．０５〜 ５．０部を含有する、乾燥したジオキサジンバイオレット顔料組成物に関する。
Hereinafter, the present invention will be described in detail.
The present invention relates to a dried dioxazine violet pigment containing 0.05 to 5.0 parts of a benzenesulfonic acid derivative and / or a benzenesulfonyl chloride derivative (B) per 100 parts of dioxazine violet pigment (A) on a mass basis. Relates to the composition.
本発明におけるジオキサジンバイオレット顔料（Ａ）とは、Ｃ．Ｉ．ピグメントバイオレット２３であり、下記化学構造式の有機顔料を意味する。 The dioxazine violet pigment (A) in the present invention is C.I. I. Pigment Violet 23, which means an organic pigment having the following chemical structural formula.
このジオキサジンバイオレット顔料（Ａ）は、公知慣用の方法にて製造することが出来る。顔料の製造方法としては、例えば、ソルベントソルトミリング法やソルベント法が、よく知られている。これらの方法は、下記の通りである。 This dioxazine violet pigment (A) can be produced by a known and commonly used method. As a method for producing a pigment, for example, a solvent salt milling method and a solvent method are well known. These methods are as follows.
ソルベントソルトミリング法は、例えば、ジオキサジンバイオレット粗顔料を食塩のような水溶性の磨砕助剤とポリエチレングリコールのような湿潤剤を併用してニーダー、バンバリーミキサー等によって磨砕した後、水洗、乾燥する方法である。一方、ソルベント法としては、例えば、ジオキサジンバイオレット粗顔料を、ボールミル、アトライターや振動ボールミル等で乾式磨砕して得られる乾式磨砕物（粉砕粗顔料組成物）を、アルコール類と水の混合溶媒、ケトン類と水の混合溶媒、または芳香族溶媒と水の混合溶媒と共に、常圧下加熱し、濾過、洗浄、乾燥する方法である。 Solvent salt milling method is, for example, using a dioxazine violet crude pigment in combination with a water-soluble grinding aid such as sodium chloride and a wetting agent such as polyethylene glycol by a kneader, Banbury mixer, etc., followed by washing with water, It is a method of drying. On the other hand, as a solvent method, for example, a dry milled product (crushed crude pigment composition) obtained by dry milling dioxazine violet crude pigment with a ball mill, attritor or vibrating ball mill, etc., and mixing alcohol and water This is a method of heating, filtering, washing and drying together with a solvent, a mixed solvent of ketones and water, or a mixed solvent of an aromatic solvent and water under normal pressure.
ジオキサジンバイオレット顔料の製造方法としては、ソルベントソルトミリング法に比べて、単位時間当たりの生産性、単位収量当たりの消費エネルギー、製造に必要な装置のメンテナンス頻度等を、より低減出来る点でソルベント法を採用することが好ましい。 Compared with the solvent salt milling method, the dioxazine violet pigment production method is a solvent method in that productivity per unit time, energy consumption per unit yield, equipment maintenance frequency required for production, etc. can be further reduced. Is preferably adopted.
ソルベント法は、質量基準でジオキサジンバイオレット粗顔料１００部と、アルコール類と水の混合溶媒、ケトン類と水の混合溶媒または芳香族溶媒と水の混合溶媒の４００〜１，０００部とを混合し、加熱することにより行うことが出来る。この際のアルコール類としては、例えばｎ−ブタノール、イソブタノール等が、ケトン類としては、例えば、メチルイソブチルケトンが、芳香族溶媒としては、例えば、トルエン、キシレン等が挙げられる。質量基準でアルコール類と水または芳香族溶媒と水との割合は、例えば、アルコール類または芳香族溶媒／水＝１５／８５〜８５／１５とすることが出来る。加熱条件は特に制限されるものではないが、例えば、３２３Ｋ（ケルビン温度）以上共沸温度、１〜８時間である。 In the solvent method, 100 parts of dioxazine violet crude pigment and 400 to 1,000 parts of a mixed solvent of alcohols and water, a mixed solvent of ketones and water, or a mixed solvent of aromatic solvent and water are mixed on a mass basis. However, it can be performed by heating. In this case, examples of alcohols include n-butanol and isobutanol, examples of ketones include methyl isobutyl ketone, and examples of aromatic solvents include toluene and xylene. The ratio of alcohol and water or aromatic solvent and water on a mass basis can be, for example, alcohol or aromatic solvent / water = 15/85 to 85/15. The heating conditions are not particularly limited, but are, for example, 323 K (Kelvin temperature) or higher, an azeotropic temperature, and 1 to 8 hours.
ジオキサジンバイオレット顔料（Ａ）としては、例えば、一次粒子径が０．０５〜０．１μｍであり且つＢＥＴ比表面積が５０〜１３０ｍ２／ｇであるものが好適に使用される。 As the dioxazine violet pigment (A), for example, those having a primary particle diameter of 0.05 to 0.1 μm and a BET specific surface area of 50 to 130 m 2 / g are preferably used.
ここで、一次粒子径とは、透過型電子顕微鏡又は走査型電子顕微鏡で視野内の粒子を撮影し、二次元画像上の凝集体を構成する顔料一次粒子の５０個につき、その最大径（長径）を各々求め、それを平均した値である。一方、ＢＥＴ比表面積とは、日本工業規格ＪＩＳ Ｚ８８３０の付属書２に規定する「１点法による気体吸着量の測定方法」に従って測定した粉末の比表面積値である。このＢＥＴ比表面積は、例えば、マイクロ・データ（株）製マイクロソープ自動表面積計MODEL4232IIの様な装置により測定することが出来る。 Here, the primary particle diameter is the maximum diameter (major diameter) of 50 primary particles of the pigment constituting the aggregate on the two-dimensional image obtained by photographing particles in the field of view with a transmission electron microscope or a scanning electron microscope. ) Are obtained and averaged. On the other hand, the BET specific surface area is a specific surface area value of the powder measured according to “Measurement method of gas adsorption amount by one-point method” defined in Appendix 2 of Japanese Industrial Standard JIS Z8830. This BET specific surface area can be measured by an apparatus such as a micro soap automatic surface area meter MODEL4232II manufactured by Micro Data Co., Ltd., for example.
ベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体（Ｂ）とは、ベンゼン又はハロゲン原子、アルキル基、ニトロ基のいずれかを含有する置換ベンゼンであって、そのベンゼン環に更にスルホン酸基（ＳＯ３Ｈ）又はスルホニルクロライド基（ＳＯ２Ｃｌ）の少なくとも一種類の官能基を含有する化合物である。ベンゼンスルホン酸誘導体は、結晶水（水和水）を含んでいても良い。この結晶水（水和水）を含むベンゼンスルホン酸誘導体は、水和物と言うこともある。結晶水（水和水）と、後記する吸湿による水分は、区別される。本発明においてこれら誘導体（Ｂ）としては、常温固体である化合物が好ましいが、常温液体の化合物も使用できる。尚、これら誘導体（Ｂ）には、ジオキサジンバイオレット顔料のスルホン酸誘導体やジオキサジンバイオレット顔料のフタルイミド誘導体等の、各種ジオキサジンバイオレット顔料の誘導体等は包含されない。 The benzenesulfonic acid derivative and / or benzenesulfonyl chloride derivative (B) is benzene or a substituted benzene containing any one of a halogen atom, an alkyl group and a nitro group, and a sulfonic acid group (SO 3) is further added to the benzene ring. H) or a compound containing at least one functional group of a sulfonyl chloride group (SO 2 Cl). The benzenesulfonic acid derivative may contain crystal water (hydration water). This benzenesulfonic acid derivative containing crystal water (hydration water) is sometimes referred to as a hydrate. Crystal water (hydration water) is distinguished from moisture due to moisture absorption described later. In the present invention, these derivatives (B) are preferably compounds that are solid at room temperature, but compounds that are liquid at room temperature can also be used. These derivatives (B) do not include derivatives of various dioxazine violet pigments such as sulfonic acid derivatives of dioxazine violet pigments and phthalimide derivatives of dioxazine violet pigments.
ベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体（Ｂ）としては、例えば、下記の様な、結晶水を含んでいても良い式（１）で表される化合物や、式（２）で表される化合物がある。結晶水（水和水）は、例えば、０．１〜１０である。 Examples of the benzenesulfonic acid derivative and / or benzenesulfonyl chloride derivative (B) include the following compounds represented by the formula (1) which may contain water of crystallization and the formula (2). There are compounds. Crystal water (hydration water) is 0.1-10, for example.
式（１） Formula (1)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、同一でも異なっていても良い、分岐していても良い炭素原子数１〜４のアルキル基、ニトロ基、ハロゲン原子、水素原子又はＳＯ３Ｈを表す。但し、Ｒ１〜Ｒ６のいずれか一つはＳＯ３Ｈである。） (Wherein R1, R2, R3, R4, R5 and R6 may be the same or different, may be branched alkyl groups having 1 to 4 carbon atoms, nitro groups, halogen atoms, hydrogen atoms or Represents SO 3 H. However, any one of R1 to R6 is SO 3 H.)
式（２） Formula (2)
（式中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５及びＲ６は、同一でも異なっていても良い、分岐していても良い炭素原子数１〜４のアルキル基、ニトロ基、ハロゲン原子、水素原子又はＳＯ２Ｃｌを表す。但し、Ｒ１〜Ｒ６のいずれか一つはＳＯ２Ｃｌである。） (Wherein R1, R2, R3, R4, R5 and R6 may be the same or different, may be branched alkyl groups having 1 to 4 carbon atoms, nitro groups, halogen atoms, hydrogen atoms or Represents SO 2 Cl, provided that any one of R 1 to R 6 is SO 2 Cl.)
この様な、結晶水を含んでいても良い式（１）で示されるベンゼンスルホン酸誘導体としては、例えば、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、ｍ−ニトロベンゼンスルホン酸、ｍ−クロロベンゼンスルホン酸等が挙げられる。式（２）で表されるベンゼンスルホニルクロライド誘導体としては、例えば、ベンゼンスルホニルクロライド、ｐ−トルエンスルホニルクロライド、ｍ−ニトロベンゼンスルホニルクロライド、ｐ−ニトロベンゼンスルホニルクロライド、ｐ−クロロベンゼンスルホニルクロライド等が挙げられる。これら誘導体（Ｂ）は、単独で使用することも二種以上を混合して使用することもできる。 Examples of the benzenesulfonic acid derivative represented by the formula (1) which may contain crystal water include benzenesulfonic acid, p-toluenesulfonic acid, m-nitrobenzenesulfonic acid, m-chlorobenzenesulfonic acid, and the like. Is mentioned. Examples of the benzenesulfonyl chloride derivative represented by the formula (2) include benzenesulfonyl chloride, p-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, p-nitrobenzenesulfonyl chloride, p-chlorobenzenesulfonyl chloride and the like. These derivatives (B) can be used alone or in admixture of two or more.
これら誘導体（Ｂ）は、中でも、結晶水を含んでいても良いベンゼンスルホン酸及び／又はトルエンスルホン酸であるか、或いは、ベンゼンスルホニルクロリド及び／又はトルエンスルホニルクロリドであることが、特に好ましい。 These derivatives (B) are particularly preferably benzene sulfonic acid and / or toluene sulfonic acid which may contain water of crystallization, or benzene sulfonyl chloride and / or toluene sulfonyl chloride.
本発明の顔料組成物は、質量基準でジオキサジンバイオレット顔料（Ａ）１００部当たり、ベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体（Ｂ）０．０５〜５．０部、好ましくは０．５〜３．０部を含有する。ベンゼンスルホン酸誘導体として、結晶水を含有するベンゼンスルホン酸誘導体を用いる場合には、結晶水を含めて前記部数の範囲となる様にする。 The pigment composition of the present invention is 0.05 to 5.0 parts, preferably 0.5 to benzenesulfonic acid derivative and / or benzenesulfonyl chloride derivative (B) per 100 parts of dioxazine violet pigment (A) on a mass basis. Contains ~ 3.0 parts. When a benzenesulfonic acid derivative containing crystallization water is used as the benzenesulfonic acid derivative, the number of parts is adjusted to include the crystallization water.
本発明の顔料組成物においては、これら誘導体（Ｂ）の使用量が前記した範囲より少ないと、光沢向上や低粘度化の効果が小さくなるし、逆に使用量が前記した範囲を越えると、光沢向上や低粘度化の効果は前記した範囲の場合に比べて大きくならない上に、酸性が強くなり、設備の腐食が促進され好ましくない。 In the pigment composition of the present invention, if the amount of these derivatives (B) used is less than the above range, the effect of improving gloss and reducing the viscosity is reduced, and conversely if the amount used exceeds the above range, The effect of improving gloss and lowering viscosity is not increased as compared with the above range, and the acidity becomes strong, and the corrosion of the equipment is promoted.
本発明の顔料組成物は、ジオキサジンバイオレット顔料（Ａ）とベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体（Ｂ）とを前記した質量割合となる様に混合することで調製することが出来る。 The pigment composition of the present invention can be prepared by mixing the dioxazine violet pigment (A) and the benzenesulfonic acid derivative and / or the benzenesulfonyl chloride derivative (B) so as to have the mass ratio described above.
本発明の顔料組成物の調製方法としては、例えば、以下の様な調製方法が挙げられる。
（Ｗ）ジオキサジンバイオレット顔料（Ａ）のウエットケーキを水等に懸濁させた顔料スラリーに前記誘導体（Ｂ）を加えて、均一に攪拌した後、常法に従って濾過、乾燥、粉砕してジオキサジンバイオレット顔料組成物とする方法。
（Ｘ）ジオキサジンバイオレット顔料（Ａ）のウエットケーキを乾燥する前に、前記誘導体（Ｂ）の水溶液をウエットケーキに噴霧して、常法に従って乾燥、粉砕してジオキサジンバイオレット顔料組成物とする方法。
（Ｙ）乾燥したジオキサジンバイオレット顔料（Ａ）と、前記誘導体（Ｂ）とを、磨砕することなく、ナウターミキサー、ヘンシェルミキサー、エアーミックス混合機、ニーダー等の配合機を用いて乾式混合する方法。
（Ｚ）予め各々別個に準備した、ジオキサジンバイオレット乾燥顔料（Ａ）と、前記誘導体（Ｂ）とを、インキ、塗料等に使用するときに同時に加える方法。
As a preparation method of the pigment composition of this invention, the following preparation methods are mentioned, for example.
(W) The derivative (B) is added to a pigment slurry obtained by suspending a wet cake of dioxazine violet pigment (A) in water or the like, stirred uniformly, filtered, dried and ground according to a conventional method. A method for producing an oxazine violet pigment composition.
(X) Before drying the wet cake of the dioxazine violet pigment (A), the aqueous solution of the derivative (B) is sprayed on the wet cake, dried and pulverized according to a conventional method to obtain a dioxazine violet pigment composition. Method.
(Y) The dry dioxazine violet pigment (A) and the derivative (B) are dry-mixed using a blender such as a Nauter mixer, a Henschel mixer, an air mix mixer, or a kneader without grinding. how to.
(Z) A method in which the dioxazine violet dry pigment (A) and the derivative (B), which are separately prepared in advance, are added simultaneously when used in ink, paint or the like.
前記した顔料組成物の調製方法では、前記（Ｗ）の顔料の調製方法が特に好ましい。 In the above-described method for preparing a pigment composition, the method for preparing a pigment (W) is particularly preferable.
本発明の顔料組成物は、乾燥した顔料組成物である。本発明においては、粉体としての形態を有している限り「乾燥した」という状態を満たすが、より正確には、日本工業規格ＪＩＳ Ｋ５１０１−１９９１に規定される「顔料試験方法」の２３に従って測定したときの顔料組成物の加熱減量が５％未満である状態を言う。加熱による減量の主原因は、吸湿による水分等である。加熱減量をゼロとすることは比較的難しいので、本発明における顔料組成物の加熱減量は、中でも３％未満であることが好ましく、特に０．１〜１．０％であることが最も好ましい。この「顔料試験法」においては、試料の顔料組成物を３７８±２Ｋ（ケルビン温度）の温度に保った乾燥器で２時間乾燥する。「加熱減量」は次式によって算出される。この加熱減量が小さい程、乾燥の程度は高いと言うことが出来る。尚、粉体の形態を有している限り、また得られる顔料組成物やインキ、塗料等に使用する上で不都合が生じない限りにおいて、水の様な液媒体を含有した状態で使用することも出来る。 The pigment composition of the present invention is a dried pigment composition. In the present invention, as long as it has a form as a powder, it satisfies the state of “dry”. More precisely, according to 23 of “Pigment Test Method” defined in Japanese Industrial Standard JIS K5101-1991. The state in which the loss on heating of the pigment composition when measured is less than 5%. The main cause of weight loss due to heating is moisture due to moisture absorption. Since it is relatively difficult to make the heating loss zero, the heating loss of the pigment composition in the present invention is preferably less than 3%, and most preferably 0.1 to 1.0%. In this “pigment test method”, a pigment composition of a sample is dried for 2 hours in a drier maintained at a temperature of 378 ± 2 K (Kelvin temperature). “Heating loss” is calculated by the following equation. It can be said that the smaller the loss on heating, the higher the degree of drying. In addition, as long as it has a powder form, and as long as there is no inconvenience when used in the resulting pigment composition, ink, paint, etc., it should be used in a state containing a liquid medium such as water. You can also.
〔但し式中、Ｗは加熱減量（％），ｍ０は試料の質量（ｇ），ｍ１は試料の乾燥後の質量（ｇ）である。〕 [Wherein, W is weight loss by heating (%), m 0 is the mass (g) of the sample, and m 1 is the mass (g) after drying the sample. ]
この様に本発明においては、顔料組成物を調製するための両原料として、結晶水を除いて、いずれも吸湿による水分等を極力含有しない、ジオキサジンバイオレット顔料（Ａ）と、ベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体（Ｂ）を用いることが好ましい。 As described above, in the present invention, the dioxazine violet pigment (A) and the benzenesulfonic acid derivative, which do not contain water or the like due to moisture absorption as much as possible, except for crystal water, as both raw materials for preparing the pigment composition And / or benzenesulfonyl chloride derivative (B) is preferably used.
本発明のジオキサジンバイオレット顔料組成物は、そこに含まれる誘導体が、従来公知のジオキサジンバイオレット顔料スルホン酸誘導体やジオキサジンバイオレット顔料フタルイミド誘導体に比べて少量でも光沢向上に効果があるだけでなく、耐ブリード性及び流動性の向上にも効果があり、ジオキサジンバイオレット顔料の誘導体に比べて安価であり、コストダウンが可能になる利点がある。 The dioxazine violet pigment composition of the present invention is not only effective in improving the gloss even if the derivative contained therein is in a small amount as compared with a conventionally known dioxazine violet pigment sulfonic acid derivative or dioxazine violet pigment phthalimide derivative, It is also effective in improving bleeding resistance and fluidity, and is advantageous in that it is less expensive than a dioxazine violet pigment derivative and can be reduced in cost.
こうして得られた本発明のジオキサジンバイオレット顔料組成物は、例えば、印刷インキ、塗料、着色成形品、静電荷像現像用トナー、液晶表示装置のカラーフィルター、インクジェット記録用水性インク等の公知慣用の各種用途に使用することが出来る。 The dioxazine violet pigment composition of the present invention thus obtained is, for example, known and commonly used printing inks, paints, colored molded articles, electrostatic charge image developing toners, liquid crystal display color filters, inkjet recording water-based inks, and the like. It can be used for various purposes.
以下、実施例及び比較例を用いて本発明を更に詳細に説明する。以下の実施例及び比較例において特に断りの無い限り、「％」は『質量%』を表すものとする。また、「温度」は特に断りの無い限り『ケルビン温度』を表すものとする。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following Examples and Comparative Examples, “%” represents “% by mass” unless otherwise specified. “Temperature” represents “Kelvin temperature” unless otherwise specified.
攪拌機、温度計、加熱装置を備えた２，０００Ｌビーカーに、充分水洗して不純物を除去された、ジオキサジンバイオレット顔料ウエットケーキ（ジオキサジンバイオレット顔料を純分で５０ｇ含む。）と水１，６００ｇを加えて、３２３Ｋで塊が無くなるまで解膠して顔料スラリーとした。
次いで、ｐ−トルエンスルホン酸１水和物〔和光純薬（株）製試薬特級。前記式（１）中、Ｒ１はメチル基、Ｒ４はＳＯ３Ｈ、その他のＲはいずれも水素原子であり、水和水１モルを含有する物質。〕１．０ｇを水１００ｇに溶解して、これを前記ジオキサジンバイオレット顔料スラリーに加えて、同温度で１時間攪拌した。常法に従ってスラリーの濾過を行い、ウエットケーキを濾別した。
このウエットケーキを３７８Ｋで１５時間乾燥、粉砕し加熱減量が０．１〜１．０％の範囲にあり、ｐ−トルエンスルホン酸を２％含有する、粉末で紫色のジオキサジンバイオレット顔料組成物４９ｇを得た。この顔料組成物は、一次粒子径が０．０５〜０．１μｍであり且つＢＥＴ比表面積が５０〜１３０ｍ２／ｇの範囲内にあった。
後記する方法に従って、ニトロセルロース（ＮＣ）フレキソ印刷インキのザーンカップ粘度、光沢と耐ブリード性評価を行った。これらの結果を併せて表１に示した。
A 2,000 L beaker equipped with a stirrer, a thermometer, and a heating device was thoroughly washed with water to remove impurities, and the dioxazine violet pigment wet cake (containing 50 g of dioxazine violet pigment in a pure amount) and 1,600 g of water. Was added and pulverized at 323K until no lumps were formed to obtain a pigment slurry.
Subsequently, p-toluenesulfonic acid monohydrate [reagent special grade manufactured by Wako Pure Chemical Industries, Ltd. In the formula (1), R1 is a methyl group, R4 is SO 3 H, and other Rs are all hydrogen atoms and contain 1 mol of hydrated water. ] 1.0 g was dissolved in 100 g of water, and this was added to the dioxazine violet pigment slurry and stirred at the same temperature for 1 hour. The slurry was filtered according to a conventional method, and the wet cake was filtered off.
This wet cake was dried and pulverized at 378 K for 15 hours, and the weight loss on heating was in the range of 0.1 to 1.0%, and the powdery purple dioxazine violet pigment composition containing 2% of p-toluenesulfonic acid 49 g Got. This pigment composition had a primary particle diameter of 0.05 to 0.1 μm and a BET specific surface area of 50 to 130 m 2 / g.
According to the method described later, the Zahn cup viscosity, gloss and bleed resistance of the nitrocellulose (NC) flexographic printing ink were evaluated. These results are shown together in Table 1.
＜比較例１＞
ｐ−トルエンスルホン酸１水和物を使用しない以外は実施例１と同様な操作によって、加熱減量が０．１〜１．０％の範囲にある、粉末で紫色のジオキサジンバイオレット顔料組成物４９ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表１に示した。
<Comparative Example 1>
49 g of a powdery purple dioxazine violet pigment composition having a loss on heating in the range of 0.1 to 1.0% by the same operation as in Example 1 except that p-toluenesulfonic acid monohydrate is not used. Got.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 1.
＜比較例２＞
ｐ−トルエンスルホン酸１水和物（同前）１．０ｇに代えて、ジオキサジンバイオレットジスルホン酸ナトリウム（Ｃ．Ｉ．ピグメントバイオレット２３のジスルホン酸ナトリウム誘導体）２．５ｇを水１００ｇに懸濁して、ジオキサジンバイオレット顔料スラリーに加えて、３２３Ｋで１時間攪拌した後、塩酸でｐＨ６．０に調整した以外は実施例１と同様な操作によって、加熱減量が０．１〜１．０％の範囲にあり、ジオキサジンバイオレットジスルホン酸を５％含有する、ジオキサジンバイオレット顔料組成物５０ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表１に示した。
<Comparative example 2>
Instead of 1.0 g of p-toluenesulfonic acid monohydrate (same as above), 2.5 g of sodium dioxazine violet disulfonate (a sodium disulfonate derivative of CI pigment violet 23) was suspended in 100 g of water. In addition to dioxazine violet pigment slurry, after stirring for 1 hour at 323 K, the weight loss on heating was in the range of 0.1 to 1.0% by the same operation as in Example 1 except that the pH was adjusted to 6.0 with hydrochloric acid. The dioxazine violet pigment composition 50g containing 5% of dioxazine violet disulfonic acid was obtained.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 1.
＜比較例３＞
−粗顔料組成物の調製−
容量５リットルのアトライター（三井鉱山株式会社製の「ＭＡ−１Ｄ型」）に、３／８インチのスチールボール１５，０００ｇ、市販ジオキサジンバイオレット粗顔料（住友化学工業（株）製 Sumitone Fast Violet RL-4R Base；一次粒子径１．０〜１００μｍの範囲内、ＢＥＴ比表面積１〜１０ｍ２／ｇの範囲内、加熱減量１．２％）２７０ｇ、及びｐ−トルエンスルホン酸１水和物（同前）１３５ｇを仕込み、温度３６３Ｋ、３００回転／分で１００分間乾式磨砕して、スチールボールを取り除き、ジオキサジンバイオレット粗顔料組成物（粉砕粗顔料組成物）４０１ｇを得た。
この粗顔料組成物を用いた以外は、実施例１と同様の方法で、各種評価を試みたが、分散が出来なくて、期待した品質のインキが得られなかった。
−顔料組成物の調製−
攪拌機、温度計、コンデンサーを備えた容量１，０００ｍｌのガラス製反応器に、イソブタノール１３０ｇ、水３７０ｇ、上記比較例３で得られたジオキサジンバイオレット粗顔料組成物（粉砕粗顔料組成物）９０ｇを加えて、３６２Ｋで５時間攪拌した。その後、コンデンサーを蒸留に切り替えて、共沸温度で、イソブタノールと水を留去した。この時に、逐次流出液量に相当する水を追加して、反応器の液面を一定に保った。共沸温度が３７３Ｋに達した時点をイソブタノールの留去の終点とした。攪拌しながら、内容物を３０３Ｋまで冷却した後、内容物を濾別し３３３Ｋの温水１０００ｇで濾過物を洗浄した。このウエットケーキを３７８Ｋで１５時間乾燥し、加熱減量が０．１〜１．０％の範囲にある、粉末で紫色のジオキサジンバイオレット顔料組成物８７ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表１に示した。
<Comparative Example 3>
-Preparation of crude pigment composition-
At 5 liters of attritor ("MA-1D type" manufactured by Mitsui Mining Co., Ltd.), 35,000 inch steel ball 15,000g, commercially available dioxazine violet crude pigment (Sumitone Fast Violet manufactured by Sumitomo Chemical Co., Ltd.) RL-4R Base: within a range of primary particle diameter of 1.0 to 100 μm, within a range of BET specific surface area of 1 to 10 m 2 / g, loss on heating 1.2%) 270 g, and p-toluenesulfonic acid monohydrate ( The same as before) 135 g was charged, and dry grinding was performed at a temperature of 363 K, 300 rpm for 100 minutes to remove the steel ball, thereby obtaining 401 g of a dioxazine violet crude pigment composition (crushed crude pigment composition).
Various evaluations were attempted in the same manner as in Example 1 except that this crude pigment composition was used, but the dispersion could not be performed and an ink having the expected quality could not be obtained.
-Preparation of pigment composition-
In a 1,000 ml glass reactor equipped with a stirrer, a thermometer, and a condenser, 130 g of isobutanol, 370 g of water, and 90 g of the dioxazine violet crude pigment composition (crushed crude pigment composition) obtained in Comparative Example 3 above. And stirred at 362K for 5 hours. Thereafter, the condenser was switched to distillation, and isobutanol and water were distilled off at the azeotropic temperature. At this time, water corresponding to the amount of the effluent was successively added to keep the liquid level of the reactor constant. The time when the azeotropic temperature reached 373 K was taken as the end point of the distillation of isobutanol. While stirring, the content was cooled to 303K, the content was filtered off, and the filtrate was washed with 1000 g of hot 333K water. This wet cake was dried at 378 K for 15 hours to obtain 87 g of a powdery purple dioxazine violet pigment composition having a loss on heating in the range of 0.1 to 1.0%.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 1.
＜試験例＞
・ＮＣフレキソ印刷インキ作成方法
以下の方法により、実施例及び比較例により得られた、ジオキサジンバイオレット顔料組成物を用いて、ＮＣフレキソ印刷インキを作成した。
ジオキサジンバイオレット顔料組成物３０部にＮＣ樹脂ワニス１７０部及び１／８インチスチールビーズ３００部を加えて、ペイントシェーカーで１時間分散してＮＣフレキソ印刷インキ２００部を作成した。
<Test example>
-NC flexographic printing ink preparation method NC flexographic printing ink was prepared by the following method using the dioxazine violet pigment composition obtained by the Example and the comparative example.
170 parts of NC resin varnish and 300 parts of 1/8 inch steel beads were added to 30 parts of dioxazine violet pigment composition and dispersed for 1 hour with a paint shaker to prepare 200 parts of NC flexographic printing ink.
・ザーンカップ(Zahn cup)静置粘度の測定方法
実施例及び比較例で得られた、ＮＣフレキソ印刷インキを２９８Ｋ恒温槽に１時間静置して恒温にしたインキをザーンカップ＃５（離合社製：オリフィス径５ｍｍ）で、インキの流出が終わるまでの時間を計測した。流出時間が６０秒以上掛かるもの、及び全量が流出しないものは『測定不能』と表現した。この時間が短いほど、流動性に優れる（粘度が低い）インキと言える。
-Zahn cup static viscosity measurement method The ink obtained by leaving the NC flexographic printing ink obtained in the examples and comparative examples in a 298K constant temperature bath for 1 hour to make the temperature constant is Zahn Cup # 5 (Made by orifice: 5 mm), and the time until the outflow of ink was measured. The case where the outflow time took 60 seconds or more and the case where the entire amount did not flow out were expressed as “unmeasureable”. The shorter this time, the better the fluidity (lower viscosity) of the ink.
・ザーンカップ(Zahn cup)攪拌粘度の測定方法
実施例及び比較例で得られた、ＮＣフレキソ印刷インキを２９８Ｋ恒温槽に１時間静置して恒温にしたインキを、直径１５ｍｍの攪拌羽根を備えた攪拌機で１０００ｒｐｍ、１分間攪拌した後、ザーンカップ＃５（離合社製：オリフィス径５ｍｍ）で、インキの流出が終わるまでの時間を計測した。
・ Measurement method of Zahn cup stirring viscosity NC flexo printing ink obtained in Examples and Comparative Examples was allowed to stand in a 298K thermostatic bath for 1 hour, and was equipped with a stirring blade having a diameter of 15 mm. After stirring for 1 minute at 1000 rpm with a stirrer, the time until the outflow of the ink was measured with Zahn cup # 5 (manufactured by Kosei Co., Ltd .: orifice diameter 5 mm).
・光沢の評価方法
実施例及び比較例で得られた、ＮＣフレキソ印刷インキを０．１５ｍｍバーコーターを用いて、アセテートフィルムに展色した。この展色フィルムを光沢計(BYK Gardner製haze gloss meter)で入射角６０度、反射角６０度の光沢を測定した。比較例１で得られた光沢値を１００（標準）とし、比較例１の光沢値との比（試料の光沢値／比較例１の光沢値＊１００）で表した。
Gloss evaluation method NC flexographic printing ink obtained in Examples and Comparative Examples was developed on an acetate film using a 0.15 mm bar coater. The gloss of this color-extended film was measured with a gloss meter (haze gloss meter manufactured by BYK Gardner) at an incident angle of 60 degrees and a reflection angle of 60 degrees. The gloss value obtained in Comparative Example 1 was defined as 100 (standard), and expressed as a ratio to the gloss value of Comparative Example 1 (Gloss value of sample / Gloss value of Comparative Example 1 * 100).
・耐ブリード性の評価方法
ＮＣフレキソ印刷インキを０．１５ｍｍバーコーターを用いて、内面処理ナイロンフィルムに塗布した。この塗布膜を３ｃｍ×４ｃｍの大きさに切断して、試料片−Ｉとした。 また、白インキを塗布した内面処理ナイロンフィルムを、４ｃｍ×５ｃｍの大きさに切断して、試料片−ＩＩとした。次いで試料片−Ｉのインキ塗布面と試料片−ＩＩのフィルム面を貼り合わせ、金属板で挟んで密着させた状態で水中に浸漬し、水より昇温して沸騰後３０分間煮沸した後、試料片−ＩＩのフィルム面へのＮＣフレキソ印刷インキの着色度合いを目視判定することにより、耐ブリード性を○（良好）、Ｘ（不良）の２段階評価した。
-Evaluation method of bleed resistance NC flexographic printing ink was applied to an internally treated nylon film using a 0.15 mm bar coater. This coating film was cut into a size of 3 cm × 4 cm to obtain a sample piece-I. Moreover, the inner surface-treated nylon film coated with white ink was cut into a size of 4 cm × 5 cm to obtain a sample piece-II. Next, the ink application surface of sample piece-I and the film surface of sample piece-II were bonded together, immersed in water in a state of being closely adhered by a metal plate, heated from water and boiled for 30 minutes after boiling. By visually judging the degree of coloring of the NC flexographic printing ink on the film surface of Sample Piece-II, the bleed resistance was evaluated in two stages: ○ (good) and X (poor).
表１ Table 1
本発明のジオキサジンバイオレット顔料組成物は、優れた流動性、光沢及び耐ブリード性を兼備するのに対して、従来からの公知の方法で製造されたジオキサジンバイオレット顔料組成物は、いずれも光沢が不充分であることがわかる。 The dioxazine violet pigment composition of the present invention has excellent fluidity, gloss and bleed resistance, whereas the dioxazine violet pigment composition produced by a conventionally known method is glossy. It is understood that is insufficient.
ｐ−トルエンスルホン酸１水和物１．０ｇを０．１ｇにした以外は実施例１と同様な操作によって、加熱減量が０．１〜１．０％の範囲にあり、ｐ−トルエンスルホン酸を０．２％含有する、粉末で紫色のジオキサジンバイオレット顔料組成物４８ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表２に示した。
Except that 1.0 g of p-toluenesulfonic acid monohydrate was changed to 0.1 g, heat loss was in the range of 0.1 to 1.0% by the same operation as in Example 1, and p-toluenesulfonic acid 48 g of a powdery purple dioxazine violet pigment composition containing 0.2% of was obtained.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 2.
実施例１で使用した、ジオキサジンバイオレット顔料のウエットケーキ（同前）に、霧吹きを用いてｐ−トルエンスルホン酸１水和物１．０gを水２０ｇに溶解したｐ−トルエンスルホン酸水溶液を均一に噴霧した後乾燥、粉砕して、加熱減量が０．１〜１．０％の範囲にある、粉末で紫色のジオキサジンバイオレット顔料組成物４８ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表２に示した。
A p-toluenesulfonic acid aqueous solution in which 1.0 g of p-toluenesulfonic acid monohydrate was dissolved in 20 g of water using a spray bottle was uniformly applied to the wet cake of dioxazine violet pigment (same as above) used in Example 1. After spraying, the powder was dried and pulverized to obtain 48 g of a powdery purple dioxazine violet pigment composition having a loss on heating in the range of 0.1 to 1.0%.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 2.
実施例１で使用したジオキサジンバイオレット顔料ウエットケーキを乾燥し粉砕して、乾燥顔料を準備した。温度コントロールできるオイルの循環装置を備えた、３００ｍL双腕型ニーダー（吉田製作所（株）製）に、この乾燥顔料５０ｇと、ｐ−トルエンスルホン酸１水和物の乾燥粉末１．０ｇを加え、３０３K、６０ｒｐｍで１時間混合し、加熱減量が０．１〜１．０％の範囲にある、粉末で紫色のジオキサジンバイオレット顔料組成物４９ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表２に示した。
The dioxazine violet pigment wet cake used in Example 1 was dried and pulverized to prepare a dry pigment. 50 g of this dry pigment and 1.0 g of dry powder of p-toluenesulfonic acid monohydrate were added to a 300 mL double-arm kneader (manufactured by Yoshida Seisakusho Co., Ltd.) equipped with an oil circulation device capable of controlling the temperature. The mixture was mixed at 303K and 60 rpm for 1 hour to obtain 49 g of a powdery purple dioxazine violet pigment composition having a loss on heating in the range of 0.1 to 1.0%.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 2.
ｐ−トルエンスルホン酸１水和物を乾燥粉末で加えたのに代えて、１．０ｇを水２０ｇに溶解して加えたのと、温度を３２８Kにて、水分を蒸発させながら混合した以外は実施例４と同様な操作によって、加熱減量が４．７％である、粉末で紫色のジオキサジンバイオレット顔料組成物５０ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表２に示した。
Instead of adding p-toluenesulfonic acid monohydrate as a dry powder, 1.0 g was dissolved in 20 g of water, and the mixture was mixed at a temperature of 328 K while evaporating water. By the same operation as in Example 4, 50 g of a powdery purple dioxazine violet pigment composition having a loss on heating of 4.7% was obtained.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 2.
ｐ−トルエンスルホン酸１水和物１．０ｇに代えて、ベンゼンスルホクロリド〔和光純薬（株）製試薬特級。前記式（２）中、Ｒ１〜Ｒ５はいずれも水素原子、Ｒ６はＳＯ２Ｃｌである物質。〕１．０ｇを用いた以外は実施例１と同様な操作によって、加熱減量が０．１〜１．０％の範囲にあり、ベンゼンスルホクロリドを２％含有する、粉末で紫色のジオキサジンバイオレット顔料組成物４８ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表２に示した。
Instead of 1.0 g of p-toluenesulfonic acid monohydrate, benzenesulfochloride [special grade reagent manufactured by Wako Pure Chemical Industries, Ltd. In the formula (2), R1 to R5 are all hydrogen atoms and R6 is SO 2 Cl. In the same manner as in Example 1 except that 1.0 g was used, the powdered purple dioxazine violet contained in the range of 0.1 to 1.0% in weight loss by heating and 2% benzenesulfochloride. 48 g of a pigment composition was obtained.
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 2.
ｐ−トルエンスルホン酸１水和物１．０ｇに代えて、ｐ−トルエンスルホン酸１水和物０．５ｇとベンゼンスルホクロリド０．５ｇを併用した以外は実施例１と同様な操作によって、加熱減量が０．１〜１．０％の範囲にあり、ｐ−トルエンスルホン酸１．０％とベンゼンスルホクロリド１．０％を含有する、粉末で紫色のジオキサジンバイオレット顔料組成物４９ｇを得た。
実施例１と同様にして各種評価を行った。これらの結果を併せて表２に示した。
In place of 1.0 g of p-toluenesulfonic acid monohydrate, heating was performed in the same manner as in Example 1 except that 0.5 g of p-toluenesulfonic acid monohydrate and 0.5 g of benzenesulfochloride were used in combination. 49 g of a powdery purple dioxazine violet pigment composition having a weight loss in the range of 0.1 to 1.0% and containing 1.0% p-toluenesulfonic acid and 1.0% benzenesulfochloride was obtained. .
Various evaluations were performed in the same manner as in Example 1. These results are shown together in Table 2.
これら実施例２〜７の顔料組成物は、いずれも、一次粒子径が０．０５〜０．１μｍであり、且つＢＥＴ比表面積が５０〜１３０ｍ２／ｇであった。 All of the pigment compositions of Examples 2 to 7 had a primary particle diameter of 0.05 to 0.1 μm and a BET specific surface area of 50 to 130 m 2 / g.
表２ Table 2
本発明のジオキサジンバイオレット顔料組成物は、ジオキサジンバイオレット顔料に対して、特定量のベンゼンスルホン酸誘導体及び／又はベンゼンスルホニルクロライド誘導体を含有した、乾燥したジオキサジンバイオレット顔料組成物なので、より優れた光沢を有するばかりでなく、耐ブリード性及び流動性にも優れるという格別顕著な効果を奏する。
The dioxazine violet pigment composition of the present invention is a dried dioxazine violet pigment composition containing a specific amount of a benzenesulfonic acid derivative and / or a benzenesulfonyl chloride derivative with respect to the dioxazine violet pigment. In addition to being glossy, it has a particularly remarkable effect of being excellent in bleed resistance and fluidity.
Claims (5)
式（１）
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5884857A (en) * | 1981-11-02 | 1983-05-21 | サンド・アクチエンゲゼルシヤフト | Dioxazine compound |
| JPS62277388A (en) * | 1986-02-19 | 1987-12-02 | Sumitomo Chem Co Ltd | Production of dioxazine compound |
| JPH039960A (en) * | 1989-06-07 | 1991-01-17 | Toyo Ink Mfg Co Ltd | Preparation of pigment |
| JPH0848687A (en) * | 1994-05-30 | 1996-02-20 | Nippon Kayaku Co Ltd | Production of dioxazine compound, coloring material and plate-like crystal |
| US6709503B1 (en) * | 2002-12-19 | 2004-03-23 | Sun Chemical Corporation | Waterbased heatset offset ink compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5884857A (en) * | 1981-11-02 | 1983-05-21 | サンド・アクチエンゲゼルシヤフト | Dioxazine compound |
| JPS62277388A (en) * | 1986-02-19 | 1987-12-02 | Sumitomo Chem Co Ltd | Production of dioxazine compound |
| JPH039960A (en) * | 1989-06-07 | 1991-01-17 | Toyo Ink Mfg Co Ltd | Preparation of pigment |
| JPH0848687A (en) * | 1994-05-30 | 1996-02-20 | Nippon Kayaku Co Ltd | Production of dioxazine compound, coloring material and plate-like crystal |
| US6709503B1 (en) * | 2002-12-19 | 2004-03-23 | Sun Chemical Corporation | Waterbased heatset offset ink compositions |
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