Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B19/00—Oxazine dyes
  • C09B19/02—Bisoxazines prepared from aminoquinones
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks

Definitions

• the present disclosure relates to a carbazole-dioxazine pigment.
• Carbazole-dioxazine pigments are well known for their strong bluish-red to violet shade. These pigments have excellent heat resistance, light resistance and tinctorial strength. These pigments are used in the applications such as paint, plastic, inks, coatings and the like.
• Pigment Violet 23 (PV-23) is the most important member of this class. Pigment violet-23 (carbazole violet) exhibits color range between bluish-red and violet shade.
• R is Ci-Cg alkyl group, preferably R is an ethyl group, R] is a chloro group, and
• the pigment of Formula-I has maximum absorption wavelength ( m a x ) at 571nm in dimethylformamide as a solvent.
• the pigment of Formula-I has molecular weight of 831 , whereas the molecular weight of PV-23 is 589.
• the pigment of the present disclosure exhibits a reddish-violet shade.
• Pigment violet-23 exhibits color range between bluish-red and violet shade.
• R is Ci-Cg alkyl group, preferably R is an ethyl group, R ⁇ is a chloro group, and
• the present disclosure provides a high molecular weight carbazole-dioxazine pigment and a method for its preparation.
• a high molecular weight homologue of a carbazole-dioxazine pigment, Pigment Violet-23 Particularly, the present disclosure provides a novel pigment having one benzamido group in each carbazole rin of Pigment Violet-23, which is represented by Formula-I.
• R is C r C 8 alkyl group, preferably R is an ethyl gro p, Ri is a chloro group, and
• the pigment of Formula- 1 has maximum absorption wavelength ( ⁇ ) at 571nm in dimethylformamide as a solvent.
• the pigment has molecular weight of 831 , whereas the molecular weight of PV- 23 is 589.
• the pigment of the present disclosure is found to have the CIE attributes of lightness (L*): 56.43, chroma (C*): 19.03, hue (h*): 287.16 and colour (a*, b*): (5.615, -18.18) and exhibits a reddish-violet shade.
• Pigment violet-23 exhibits color range between bluish-red and violet shade.
• the first step is nitration of 3-nitro-N-ethylcarbazole to form 3,6-dinitro-N- ethylcarbazole which is then reduced to form 3-amino-6-nitro-N-ethylcarbazole.
• This amino compound is further benzoylated to form 3-benzamido-6-nitro-N- ethylcarbazole which is hydrogenated to form 6-amino-3-benzamido-N- ethylcarbazole.
• Condensation of 6-amino-3-benzamido-N-ethylcarbazole with chlroanil provides an intermediate. Cyclization of the intermediate using a cyclization reagent provides the pigment of Formula-I.
• the process involves the following steps:
• the first step (step-a) is nitration of 3-nitro-N-ethyl-carbazole to form 3,6- dinitro-N-ethylcarbazole.
• the nitration is carried out using nitric acid in the presence sodium nitrite and at least one solvent selected from a group consisting of monochlorobenzene and orthodichlorobenzene.
• the nitration is carried out at a temperature ranging from 60 to 100°C.
• step-b 3,6-dinitro-N-ethylcarbazole is reduced to form 3- amino-6-nitro-N-ethylcarbazole.
• Step-b The reduction is carried out using sodium hydrosulfide and at least one solvent selected from a group consisting of ethanol and methanol.
• the reduction is carried out at a temperature ranging from 55 to 80°C.
• step (step-c) is benzoylation of 3-amino-6-nitro-N-ethylcarbazole to form
• the benzoylation is carried out using benzoyl chloride and at least one solvent selected from a group consisting of o-dichlorobenzene and monochlorobenzene.
• the benzoylation is carried out at a temperature ranging from 80 to 120°C.
• step-d is hydrogenation of 3-benzamido-6-nitro-N- ethylcarbazole to form 6-amino-3-benzamido-N-ethylcarbazole.
• the hydrogenation is carried out in the presence of raney nickel as a catalyst and sodium phosphate dibasic.
• the hydrogenation is carried out in at least one solvent selected from a group consisting of dimethylacetamide and methanol.
• step-e 6-amino-3-benzamido-N-ethylcarbazole and chlroanil are condensed to form an intermediate of Formula II.
• R is Q-Cs alkyl group, preferably R is an ethyl group, Ri is a chloro group, and
• the condensation is carried out using sodium acetate and at least one solvent selected from a group consisting of o-dichlorobenzene and monochlorobenzene.
• the condensation is carried out at a temperature ranging from 50 to 75 °C.
• the intermediate of Formula-II is cyclized in the presence of a cyclization reagent to obtain the pigment of Formula I (step-f).
• the cyclization reagent used is benzenesulfonyl chloride.
• the cyclization is carried out in at least one solvent selected from a group consisting of o- dichlorobenzene, nitrobenzene.
• the cyclization is carried out at a temperature ranging from 160 to 180°C.
• the maximum visible absorption spectrum of the pigment of Formula- 1 in dimethylformamide as a solvent is found at 571nm. Further, the study of colour values of the pigment draw-downs are carried out.
• the CIE attributes of lightness (L*), chroma (C*), hue (h*) and colour (a*, b*) are determined by colorimetric assessment of pigment drawdown.
• Step a (Preparation of 3,6-dinitro-N-ethylcarbazole (DNEC)): 1440gms (6.0moles) of 3-Nitro-N-ethylcarbazole (NEC) was charged in to a reactor vessel containing monochlorobenzene (4800ml) and 4.8gms (0.069moles) of sodium nitrite. The mixture was then stirred at a temperature of 30°C. 26 ml nitric acid (9.0moles) was added to the mixture and the mixture was then heated to a temperature of 80°C. 800ml of nitric acid was further added to the mixture over a period of 6-9 hours maintaining the temperature of 80°C.
• NEC 3-Nitro-N-ethylcarbazole
• DNEC 3,6-Dinitro-N-ethylcarbazole
• Crude DNEC was purified by dissolving in nitrobenzene ( ⁇ lgm/ml of nitrobenzene) at a temperature of 160°C followed by cooling and filtering to obtain a cake. Further, re-slurring the cake in methanol ( ⁇ 0.95ml/gm of cake) at ambient temperature provided pure DNEC of purity 98.6%. The yield of dried product (DNEC) was 1 109 gms (64.8%).
• Step-b Preparation of 3-amino-6-nitro-N-ethylcarbazole: Sodium hydrosulfide (NaSH)-ethanol solution was prepared by vacuum drying 200 gm of 30% NaSH to remove water and treating it with 200 ml ethanol. To 150 ml of NaSH- ethanol solution so obtained, 100 gm of pure DNEC was charged and the mixture was heated to 70°C. Further quantity of 1 10 ml of NaSH ethanol solution was then added slowly to the mixture. Reaction was maintained at 70°C for 6-7 hours to yield 50% of Aminonitroethylcarbazole (purity 98.3%, DNEC 0.2% and DAEC 0.3%). Elemental analysis of the product so obtained is as follows:
• Step-c (Benzoylation of 3-amino-6-nitro-N-ethylcarbazole): A mixture containing 43.2gms (0.169moles) of 3-amino-6-nitro-N-ethylcarbazole and 350ml orthodichlorbenzene was heated to 100°C. 29 gms (0.203moles) of benzoyl chloride was added to the mixture over a period of 1 hour and the reaction was continued at 100°C. During the reaction evolution of hydrochloric gas was observed. The reaction was carried out for 9-10 hours to yield 87% benzoylated derivative (3-nitro-6-benzoylamino ethyl carbazole) having purity 98.2%. Elemental analysis of the product so obtained is as follows: Elemental %C %H %N %o
• Step-d (Hydrogenation of 3-benzamido-6-nitro-N-ethylcarbazole): 50 gms (0.139moles) of 3-nitro-6-benzoylamino-N-ethylcarbazole was hydrogenated in the presence of 600ml of dimethylacetamide (DMAc), lOg sodium phosphate dibasic and 20gm (wet) Raney Nickel at a temperature of 125°C and at a pressure of lOKg/cm for a period of 10-1 1 hours to yield 82% of the crude hydrogenated product (purity 85-89%). Crude product was recrystallized from DMAc to yield hydrogenated product, 3-amino-6-benzoylamino ethyl carbazole of 95% purity. Molecular weight and structure was confirmed by MS, NMR and IR spectra.
• Steps-e and f Preparation of pigment of Formula- 1): 50gms of 3-amino-6- benzoylamino ethyl carbazole (0.145 moles) and ortho-dichlorobenzene (765 ml) were charged in a reactor vessel. To the mixture 24.3gms (0.179moles) of sodium acetate and 26.8gm chloranil (0.109 moles) were added at a temperature of 40 °C, the mixture was then stirred for a period of 10 minutes and heated further to 60°C and maintained for a period of 4-6 hours. Reaction was monitored by TLC.
• acetic acid formed was removed along with ortho-dichlorobenzene by distillation at 100°C and 600mm Hg vacuum, over a period of 3-5 hours. After complete removal of acetic acid, fresh ortho-dichlorobenzene was added followed by addition of 17.2 gms of benzene sulfonyl chloride (0.097 moles). The addition was carried out drop-wise at 140°C over a period of 20min-lhr. Temperature was slowly raised to 175°C and maintained for a period of 6-7 hours to yield a cyclized product. The product mixture so formed was cooled to 90°C and then isolated by filtration.
• the filtered product was washed with hot ortho-dichlorobenzene, methanol and finally with water and then dried in oven at 80°C to yield 56gm of crude pigment (88% yield).
• the product was characterized by ⁇ -NMR, elemental analysis and IR spectra. IR spectra showed absence of amino group.
• the elemental analysis results are shown in following table.
• the dried crude pigment was kneaded with salt (sodium chloride) and DEG and treated with a solvent system containing isobutyl alcohol-water in the presence of caustic lye at a reflux temperature to yield reddish-violet shade of carbazole- pigment.
• salt sodium chloride
• DEG dimethyl methacrylate
• the following table shows colorimetric assessment of pigment drawdown.
• the novel pigment of the present disclosure exhibits reddish-violet shade.
• the pigment has the desired chemical resistance (in 2% hydrochloric acid and 2% sodium hydroxide).
• the solvent fastness (water, xylene, methyethylketone, t-butanol, MEK, toluene, butyl acetate and mineral turpentine) of the pigment of the present disclosure is found very good to excellent.

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• General Chemical & Material Sciences (AREA)
• Indole Compounds (AREA)
• Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)

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• 2013
  • 2013-06-11 IN IN1990MU2013 patent/IN2013MU01990A/en unknown
• 2014
  • 2014-06-11 EP EP14810946.5A patent/EP3008133B1/en active Active
  • 2014-06-11 WO PCT/IN2014/000388 patent/WO2014199400A2/en not_active Ceased
  • 2014-06-11 US US14/896,876 patent/US9540514B2/en active Active

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