WO2003052000A1 - Procede de production de preparations de colorants azo a fines particules pour l'impression par jet d'encre - Google Patents

Procede de production de preparations de colorants azo a fines particules pour l'impression par jet d'encre Download PDF

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Publication number
WO2003052000A1
WO2003052000A1 PCT/EP2002/012599 EP0212599W WO03052000A1 WO 2003052000 A1 WO2003052000 A1 WO 2003052000A1 EP 0212599 W EP0212599 W EP 0212599W WO 03052000 A1 WO03052000 A1 WO 03052000A1
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block
pigment
colorant
coupling
ink
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PCT/EP2002/012599
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German (de)
English (en)
Inventor
Martin Alexander Winter
Hans Joachim Metz
Franz Schui
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Clariant Gmbh
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Publication of WO2003052000A1 publication Critical patent/WO2003052000A1/fr

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    • 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
    • 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
    • C09B41/00—Special methods of performing the coupling reaction
    • C09B41/001—Special methods of performing the coupling reaction characterised by the coupling medium
    • C09B41/005—Special methods of performing the coupling reaction characterised by the coupling medium containing low molecular weight dispersing agents; containing surface active polythylene gylcols

Definitions

  • the present invention relates to a process for the production of particularly fine-particle azo colorant dispersions which can be processed into inkjet inks without additional grinding processes.
  • inks are used for thermal and piezoelectric ink-jet printing, which are based on solutions of water-soluble dyes, which is why the prints have high brilliance and optical density, but have insufficient light fastness and poor water resistance.
  • the mentioned disadvantages of dye-based ink jet inks can only be partially overcome with the help of special papers.
  • One way to overcome these drawbacks is to use pigmented inks.
  • pigmented inks for inkjet printing they must have a suitable viscosity and surface tension for printing, they must be stable in storage, i.e. they should not coagulate and the dispersed pigment should not settle, they should not clog the printing nozzles, which can be particularly problematic with the inks containing pigment particles, and they should be environmentally friendly, i.e. are largely based on water and contain the lowest possible concentrations of organic solvents.
  • High demands are also placed on the purity of the preparations, since excessive concentrations of inorganic or organic salts and ions, in particular chloride ions, cause corrosion and thus premature destruction of the print heads or, in the case of bubble jet printers, harmful deposits on the heating elements to lead.
  • the fine division of the pigment preparations is a basic requirement for them Use in ink jet printing, because in order not to clog the nozzles, the average particle size of the pigment particles should not exceed 200 nm and the particle size distribution should be very narrow, so that the maximum particle size does not exceed 500 nm. In addition to the fine particle size, the flocculation resistance is particularly important
  • the conventional production of pigmented preparations for ink-jet printing is characterized in that at least one colorant, either as a powder or as a press cake, together with at least one dispersing aid, optionally with at least one organic solvent and optionally with other customary additives in preferably deionized water pasted and then homogenized and predispersed with a dissolver or other suitable apparatus. If necessary, fine dispersion is then carried out using a bead mill or another suitable dispersing unit, fine dispersion and grinding to the desired particle size distribution. Following the fine dispersion, the dispersion is diluted to the desired colorant concentration with deionized water.
  • This method directly produces dye dispersions, which are worked up by means of a membrane separation process and further processed without grinding directly into a liquid formulation or a pasty or solid colorant preparation.
  • the cited patent describes primarily the synthesis of those azo dyes which belong to the group of disperse dyes and are suitable for dyeing and printing hydrophobic fiber materials.
  • the use of the dispersions for ink-jet printing is not described and is also not possible since the particle sizes of about 2 ⁇ m which are formed are too large for ink-jet inks.
  • the fine particle size (maximum particle sizes of the colorant particles smaller than 500 nm) of the colorant preparations is a basic requirement for them
  • EP-0 136 619 Another disadvantage of the process described in EP-0 136 619 is the preparation of the azo colorants described by simultaneous diazotization and coupling in one reaction vessel. With this approach, the reaction between the coupler and the diazonium compound is uncontrolled, which prevents the production of high quality azo pigments.
  • the invention relates to a process for the production of finely divided dispersions of insoluble to poorly soluble azo colorants, characterized in that a diazonium salt capable of coupling with a coupling component in the presence of at least 45% by weight, based on the theoretically expected amount of colorant, of a surface-active agent , couples.
  • the colorant dispersions of the invention are extremely finely divided, the maximum particle sizes that are below 500 nm, 300 nm usually below, more preferably below 200 nm, where d 5 o values are achieved nm 100th They are therefore suitable for the production of ink-jet inks without any further distribution processes. They are stable in storage over longer periods, even at elevated temperatures, and show no flocculation. A very high purity can be achieved by membrane filtration downstream of the synthesis, so that the content of inorganic salts and in particular the content of halides is very low. A low concentration of halide ions, especially chloride ions, reduces the corrosion of the ink jet printheads.
  • the insoluble to poorly soluble azo colorants are primarily azo pigments and azo disperse dyes.
  • the azo pigments are monoazo, disazo, ⁇ -naphthol, naphtol AS,
  • Diazonium salts of aromatic or heteroaromatic amines are used as reactants for the azo coupling reaction, such as, for example, aniline, 2-nitroaniline, methyl anthranilate, 2,5-dichloro-aniline, 2-methyl-4-chloroaniline, 2-trifluoromethyl-4-chloroaniline, 2, 4.5-Trichloroanilin; 3-amino-4-methylbenzamide, 4-amino-3-chloro-N'-methylbenzamide, o-toluidine, o-dianisidine, 2,2 ', 5,5'-tetrachlorobenzidine, 2-amino-5-methyl -benzenesulfonic acid and 2-amino-4-chloro-5-methyl-benzenesulfonic acid.
  • azo pigments 4-methyl-2-nitro-phenylamine, 4-chloro-2-nitro-phenylamine, 3,3-dichlorobiphenyl-4,4'-diamine, 3,3-dimethyl- biphenyl-4,4'-diamine, 4-methoxy-2-nitro-phenylamine, 2-methoxy-4-nitro-phenylamine, 4-amino-2,5-dimethoxy-N-phenylbenzenesulfonamide, 5-amino-isophthalic acid dimethyl ester , Anthranilic acid, 2-trifluoromethyl-phenylamine, 2-amino-terephthalic acid, dimethyl ester, 1, 2-bis- (2-amino-phenoxy) -ethane, 2-amino-4-chloro-5-methyl-benzenesulfonic acid, 2-methoxyphenylamine, 4 - (4-Amino-benzoylamino) benzamide, 2,4-
  • n is a number from 0 to 3
  • R 1 is a CrC 4 alkyl group, such as methyl or ethyl; a CrC alkoxy group such as methoxy or ethoxy; a trifluoromethyl group; a nitro group; a halogen atom such as fluorine, chlorine or bromine; an NHCOCH 3 group; a S0 3 H group; a SO 2 NR 10 R 11 group in which R 10 and R 11 are identical or different and denote hydrogen or dC -alkyl; a COOR 10 group in which R 10 has the meaning given above; or can be a C00NR 12 R 13 group in which R 12 and R 13 independently of one another represent hydrogen, C 1 -C 4 -alkyl or phenyl, the phenyl ring being substituted by two or three identical or different substituents from the group C 1 - C 4 alkyl, -CC 4 -A!
  • X represents hydrogen, a COOH group or a group of the general formula (III),
  • n and R 1 are as defined above;
  • Q 1 , Q 2 and Q 3 can be the same or different and N, NR 2 , CO, N-CO,
  • NR 2 -CO CO-N, CO-NR 2 , CH, N-CH, NR 2 -CH, CH-N, CH-NR 2 , CH 2 , N-CH 2 , NR 2 -CH 2> CH 2 -N, CH 2 -NR 2 or S0 2 , mean, wherein
  • R 2 represents a hydrogen atom; for a -CC 4 alkyl group, such as methyl or ethyl; or represents a phenyl group which is unsubstituted or by halogen,
  • C 1 -C 4 alkyl, CrC 4 alkoxy, trifluoromethyl, nitro, cyano can be substituted one or more times, with the proviso that the combination of Q 1 , Q 2 and Q 3 with the two carbon atoms of the phenyl ring is a saturated or unsaturated one , five or six-membered ring results;
  • R 3 is a group CH 3 , C00CH 3 or COOC 2 H 5!
  • R 4 is a group CH 3 , S0 3 H or a chlorine atom, and p is a number from 0 to 3, where p> 1 R 4 may be the same or different.
  • Monoazo, disazo, isoindoline and benzimidazolone pigments are selected as particularly preferred azo pigments, in particular the color index pigments Pigment Yellow 17, Pigment Yellow 74, Pigment Yellow 83, Pigment Yellow 97, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 151 , Pigment Yellow 155, Pigment Yellow 180, Pigment Yellow 213, Pigment Red 57: 1, Pigment Red 146, Pigment Red 176, Pigment Red 184, Pigment Red 185 or Pigment Red 269, but without the invention only for these pigments restrict.
  • the color index pigments Pigment Yellow 17, Pigment Yellow 74, Pigment Yellow 83, Pigment Yellow 97, Pigment Yellow 120, Pigment Yellow 128, Pigment Yellow 151 , Pigment Yellow 155, Pigment Yellow 180, Pigment Yellow 213, Pigment Red 57: 1, Pigment Red 146, Pigment Red 176, Pigment Red 184, Pigment Red 185 or Pigment Red 269, but without the invention only for these pigments restrict.
  • the surface-active agent is used in an amount of at least 45% by weight, preferably at least 50% by weight, in particular at least 60% by weight, particularly preferably at least 75% by weight, based on the Azo colorants used.
  • the maximum amount there are no technical limits on the maximum amount, but 500% by weight, preferably 400% by weight, in particular 300% by weight, particularly preferably 200% by weight, based on the azo colorant, are expedient and economically sensible.
  • Anionic, cationic, nonionic and amphoteric surface-active compounds are suitable as surface-active agents.
  • nonionic surfactants are alkyl or aryl alkoxylates, such as, for example, alkoxylates of castor oil rosin esters, fatty alcohols, fatty amines, fatty acids or fatty acid amides and alkoxylation products of alkylphenols or their oligomeric or polymeric derivatives, for example aldehyde condensation products.
  • Alkoxylates of styrene-phenol addition products such as 2,4,6-tris (1-phenylethyl) phenol and of diglycerol and polyglycerol esters of long-chain acids are also possible.
  • Amphiphilic polymers or copolymers can also be used as dispersants, for example block-polymethacrylic acid ester block-polyethylene oxide copolymers, block-polystyrene-block-polyethylene oxide copolymers, block-polyethylene oxide-block-polypropylene oxide copolymers, block-polyethylene-diamine-block-polyethylene oxide - Block polypropylene oxide copolymers, polyvinylpyrrolidones or polyvinyl alcohols.
  • Anionic and cationic surfactants are suitable as ionic surface-active compounds.
  • These surfactants are expediently used in the form of the alkali metal salts, ammonium salts and / or the water-soluble amine salts.
  • sulfonates of alpha-olefins sulfonates of polynaphthalenes, lignin sulfonates, dialkyl sulfosuccinates and sulfated fatty acids or oils and their salts can also be used.
  • cationic surfactants from the group of the alkyl or arylammonium salts, as well as zwitterionic surfactants or mesoionic surfactants, such as e.g. Amine oxides.
  • polymeric surface-active compounds for example acrylate resin copolymers with an average molecular weight M v between 1000 and 50,000 g / mol, consisting essentially of monoalkenyl aromatics and acrylates.
  • Monoalkenyl aromatics are understood in particular to mean monomers from the group consisting of styrene, ⁇ -methyl styrene, vinyl toluene, tert-butyl styrene, o-chlorostyrene and mixtures thereof.
  • Acrylates are monomers from the group consisting of acrylic acid, methacrylic acid and esters of acrylic or methacrylic acid. Examples are:
  • Acrylate resins composed of the monomers styrene and (meth) acrylic acid are particularly preferred according to the invention.
  • the acrylate resin is expediently used in the form of the alkali metal salts, ammonium salts or the water-soluble amine salts, preferably as a 1 to 35% by weight, in particular 5 to 30% by weight, aqueous solution.
  • the acrylate resins described above can be produced, for example, as described in US Pat. No. 4,529,787.
  • the acrylate resin used according to the invention can contain small amounts, such as 0.5 to 2 mol%, of a surface-active compound capable of polymerization in the copolymer.
  • the diazonium salts of the amines described above are used for the process according to the invention.
  • Alkali metal nitrites or the alkyl nitrites of short-chain alkanes, together with sufficiently strong mineral acids, are usually suitable for the diazotization reaction.
  • Sodium nitrite and hydrochloric acid are particularly suitable.
  • the reaction can be carried out in a temperature range from -5 ° C to 80 ° C, preferably between 5 ° C and 25 ° C.
  • non-ionic, anionic or cationic surface-active compounds can already be present during the diazotization. If necessary, other auxiliaries, such as natural or synthetic resins or resin derivatives, can also be used.
  • the coupling component can either be suspended or dissolved in water, in the presence of one or more of the surface-active agents described above and, if appropriate, various buffer and auxiliary substances and organic solvents customary in pigment chemistry.
  • the coupling component is first dissolved in a base and then by adding acid, e.g. Hydrochloric acid or acetic acid, finely dispersed.
  • acid e.g. Hydrochloric acid or acetic acid
  • the azo coupling reaction is preferably carried out in aqueous solution or suspension, but it is also possible to use organic solvents, if appropriate in a mixture with water, for example alcohols having 1 to 10 carbon atoms, such as, for example, methanol, ethanol, n-propanol, isopropanol, butanols, such as n-butanol, sec-butanol, tert-butanol, pentanols, such as n-pentanol, 2-methyl-2-butanol, hexanols, such as 2-methyl-2-pentanol, 3-methyl-3-pentanol, 2- Methyl-2-hexanol, 3-ethyl-3-pentanoI, octanols such as 2,4,4-trimethyl-2-pentanol, cyclohexanol; or glycols, such as ethylene glycol, diethylene glycol, propylene glycol, di
  • the coupling is possible by the direct or indirect procedure, but is preferably carried out directly, ie the diazonium salt is added to the coupling component.
  • the coupling reaction can be carried out in a temperature range between -5 ° C and 80 ° C, preferably between 5 ° C and 25 ° C, and at a pH between pH 4 and pH 14. in particular between pH 4.5 and pH 12.
  • the coupling component based on the amount of diazonium compound, is used in a slight excess. It is also possible to add all or part of the amount of surface-active agents according to the invention to the reaction mixture only during the coupling. A subsequent temperature treatment to temperatures of up to 100 ° C is possible to accelerate the complete coupling.
  • the resulting azo colorant dispersion advantageously has a colorant concentration of 0.1 to 10% by weight.
  • the dispersion can first be roughly filtered and then cleaned and desalinated to the desired degree by membrane filtration.
  • the colorant dispersion can then be concentrated either by distilling off the water or organic solvent and / or by membrane filtration, e.g. to a concentration of 2 to 25 wt .-%, and thus be converted into a storage-stable liquid formulation.
  • Complete drying e.g. Spray drying, into a redispersible solid
  • Water or organic solvent can also be used before membrane filtration.
  • the membranes used for this can be constructed either from organic materials or from inorganic materials.
  • organic membrane materials such.
  • Inorganic materials are, for example, those made of porous carbon, the surface of which is covered with a thin layer of zirconium oxide or aluminum oxide, or of porous glass.
  • the membranes are expediently used in tubular form, so that several tubes can be combined in tubular membrane modules.
  • the colorant dispersions produced according to the invention can contain an organic solvent or mixtures of such solvents as an additional component, these solvents optionally having a water-retaining effect.
  • Suitable solvents are, for example, monohydric or polyhydric alcohols, their ethers and esters, for example alkanols, in particular with 1 to 4 carbon atoms, for example methanol, ethanol, propanol, isopropanol, butanol, isobutanol; di- or trihydric alcohols, in particular with 2 to 6 carbon atoms, for example ethylene glycol, propylene glycol, 1,3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1, 2,6- Hexanetriol, glycerin, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol; lower alky
  • the colorant dispersions produced according to the invention may also contain further additives, in particular those customary for ink-jet inks, these likewise being added either directly before, in the course of and / or after the azo coupling or only after the concentration and / or purification step.
  • additives are, for example, preservatives, antioxidants, degassers / defoamers and agents for regulating the viscosity, for example polyvinyl alcohol, cellulose derivatives or water-soluble natural or artificial resins and polymers as film formers or binders to increase the adhesive and abrasion resistance.
  • Organic or inorganic bases and acids are used as pH regulators.
  • Preferred organic bases are amines, such as, for example, ethanolamine, diethanolamine, triethanolamine, N, N-dimethylethanolamine, diisopropylamine, aminomethylpropanol or dimethylminomethylpropanol.
  • Preferred inorganic bases are lithium, sodium, potassium hydroxide or ammonia.
  • hydrotropic compounds such as formamide, Urea, tetramethyl urea, e-caprolactam, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butyl glycol, methyl cellosolve, glycerin, sugar, N-methylpyrrolidone, 1, 3-diethyl-2-imidazolidinone, thiodiglycol, sodium benzenesulfonol sulfonate Toluene sulfonate, Na cumene sulfonate, Na benzoate, Na salicylate or Na butyl monoglycol sulfate.
  • hydrotropic compounds such as formamide, Urea, tetramethyl urea, e-caprolactam, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butyl glycol, methyl cellosolve, glycerin, sugar, N-methylpyrrolidone, 1, 3-diethyl-2-imid
  • Ink-jet inks are understood to mean both inks on an aqueous (including microemulsion inks) and non-aqueous (“solvent-based”) basis, UV-curable inks and those inks which work according to the hot-melt process.
  • Ink-jet inks on an aqueous basis essentially consist of 0.5 to 100% by weight, preferably 1 to 50% by weight, of one or more of the colorant dispersions according to the invention, 0 to 30% by weight of one or more hydrotropes, ie water-retaining compounds and / or organic solvents and possibly the rest water.
  • the water-based ink jet inks may also contain water-soluble binders and other additives, such as e.g. Surfactants and wetting agents, degassers / defoamers, preservatives and antioxidants.
  • Solvent-based ink jet inks essentially consist of 0.5 to 30% by weight of one or more of the colorant dispersions according to the invention, 70 to 95% by weight of an organic solvent and / or a hydrotropic compound.
  • the solvent-based ink-jet inks can contain carrier materials and binders which are soluble in the "solvent", such as e.g. Polyolefins, natural and synthetic rubber, polyvinyl chloride, vinyl chloride / vinyl acetate copolymers, polyvinyl butyrals, wax / latex systems or combinations of these compounds.
  • UV-curable inks essentially contain 0.5 to 30% by weight of one or more of the colorant dispersions according to the invention, 0.5 to 95% by weight
  • Water 0.5 to 95% by weight of an organic solvent, 0.5 to 50% by weight a radiation-curable binder and optionally 0 to 10% by weight of a photoinitiator.
  • Hot-melt inks are usually based on waxes, fatty acids, fatty alcohols or sulfonamides, which are solid at room temperature and become liquid when heated, the preferred melting range being between approx. 60 and approx. 140 ° C.
  • Hot melt ink jet inks essentially consist of 20 to 90% by weight of wax and 1 to 15% by weight of one or more of the colorant dispersions produced according to the invention.
  • an additional polymer as a "dye dissolver"
  • dispersing aid 0 to 20% by weight of viscosity regulators
  • plasticizer 0 to 10% by weight % Stickiness additive
  • transparency stabilizer prevents, for example, the crystallization of the wax
  • antioxidant 0 to 2% by weight antioxidant.
  • Typical additives and auxiliaries are e.g. in U.S. Patent 5,560,760.
  • the ink jet inks can be produced by adding the colorant dispersion into the microemulsion medium or into the aqueous or non-aqueous medium or into the medium for producing the UV-curable ink or into the wax for producing a hot-melt ink jet Ink is dispersed.
  • the colorant dispersions produced according to the invention can be used for printing a wide variety of different types of coated or uncoated substrate materials.
  • substrate materials for printing on cardboard, cardboard, wood and wood-based materials, metallic materials, semiconductor materials, ceramic materials, glasses, glass and ceramic fibers, inorganic materials, concrete, leather, food, cosmetics, skin and hair.
  • the substrate material can be two-dimensionally flat or spatially extended, that is to say three-dimensionally designed, and can be completely or only partially printed or coated. It was found that the colorant dispersions according to the invention have advantageous overall application properties and optimally fulfill the above-mentioned tasks and requirements in ink-jet printing.
  • the viscosity remains stable both at room temperature and when stored at 60 ° C for one week, and the particle size distribution changes only insignificantly during storage.
  • the inks made from the dispersions are characterized above all by extremely good behavior in ink-jet printing, good stability during storage and in the ink-jet printing process. Furthermore, the prints produced are characterized by their high light and water fastness.
  • the colorant dispersions prepared according to the invention are also suitable as colorants in electrophotographic toners and developers, such as e.g. One-component and two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerization toners and other special toners.
  • Typical toner binders are polymerization, polyaddition and polycondensation resins, such as e.g.
  • the colorant dispersions prepared according to the invention are also suitable as colorants in powder coatings, in particular in triboelectrically or electrostatically sprayed powder coatings, which are used for the surface coating of objects made of, for example, metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber ,
  • Epoxy resins, carboxyl- and hydroxyl-containing polyester resins, polyurethanes and acrylic resins are typically used as powder coating resins together with conventional hardeners. Combinations of resins are also used.
  • epoxy resins are often used in combination with carboxyl- and hydroxyl-containing polyester resins.
  • Hardener components are, for example, acid anhydrides, imidazoles and dicyandiamide and their derivatives, blocked isocyanates, bisacyl urethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazolines and dicarboxylic acids.
  • colorant dispersions prepared according to the invention are also suitable as colorants for color filters, both for additive and for subtractive color production.
  • parts mean parts by weight and percentages by weight.
  • a hydrochloric acid 3,3'-dichlorobenzidine dihydrochloride suspension (contains 32.6 parts of 3,3'-dichlorobenzidine dihydrochloride) are stirred in 31.7 parts of aqueous hydrochloric acid (31% w / w) and 50 parts of water. 1.4 parts of ® Tonsil are added to this suspension, then this mixture is cooled to 0 ° C. with ice, and then mixed with 34.2 parts of aqueous sodium nitrite solution (40% w / w) and 2 hours at 10 to 15 ° C. touched. The finished diazonium salt solution is then clarified via a filter and used immediately for coupling.
  • the dispersant solution described in Example 1 is used as the dispersant.
  • the entire amount of diazonium salt solution from b) is then added dropwise under the surface of the coupler suspension at a temperature of 20 ° C. in the course of 1 hour, the pH being between pH 4.5 by metered addition of an aqueous sodium hydroxide solution (6% w / w) and pH 5.0 is maintained.
  • the nanodisperse pigment dispersion obtained (P.Yellow 126) is adjusted to a pH of 7.0 with aqueous sodium hydroxide solution (6% w / w) and filtered (pore size of the filter approx. 100 ⁇ m) in order to exclude coarse impurities.
  • An aqueous solution of an acrylate resin neutralized with sodium hydroxide is used, which is characterized by the following features: Structure: random copolymer of styrene and acrylic acid
  • acrylate solution 61 parts of sodium hydroxide are first dissolved in 1080 parts of deionized water. Then 400 parts of the polyacrylate resin are added at 60 ° C. and the mixture is stirred at this temperature until it is completely dissolved.
  • aqueous sodium nitrite solution (40% w / w) are added below the surface within 10 minutes, the temperature remaining in a range between 0 ° C. and 10 ° C.
  • the mixture is stirred at a temperature between 10 ° C. and 18 ° C. for about 15 minutes.
  • the excess nitrite is then removed by adding amidosulfonic acid, and the solution obtained is clarified using a filter.
  • the nanodisperse pigment dispersion obtained which has a pH of 6.2, is stirred at about 10 to 20 ° C. for about 1 hour until there is no longer any excess diazo.
  • the dispersion (P.Yellow 180) is then adjusted to pH 8 with aqueous sodium hydroxide solution (33 w / w) and filtered (pore size of the filter approx. 100 ⁇ m) to rule out coarse impurities.
  • the acrylate resin solution described in Example 3 is used as the dispersant. Furthermore, a tallow fatty alcohol alkoxylate, made from 1 mol tallow fatty alcohol and 25 mol ethylene oxide, is used.
  • N-acetoacetyl-6-methoxy-7-amino-quinoxaline-2,3-dione are stirred in 400 parts of water within about 12 hours and then dissolved in 45 parts of aqueous sodium hydroxide solution (33% w / w).
  • aqueous sodium hydroxide solution 33% w / w.
  • demineralized water 22.8 parts of acetic acid (100% w / w) and 16 parts of that described under a) Tallow fatty alcohol ethoxylates (10% w / w) submitted.
  • the N-acetoacetyl-6-methoxy-7-amino-quinoxaline-2,3-dione solution is added dropwise to this template at a temperature between 0 ° C.
  • the diazonium salt solution b) is added dropwise below the surface within 1 hour at 10 to 20 ° C., the pH being determined by metered addition of a mixture of 408.8 parts of the a) described aqueous acrylate solution in 600 parts of water and 65 parts of aqueous sodium hydroxide solution (6% w / w) is kept between pH 7.4 and pH 7.5.
  • the nanodisperse pigment dispersion obtained (P.Yellow 213), which has a pH of 7.3, is stirred at 20 ° C. for about 1 hour until the excess diazo is no longer detectable.
  • the dispersion is then filtered (pore size of the filter approx. 100 ⁇ m) to exclude coarse impurities.
  • Example 3 has been described.
  • the suspension obtained is mixed with 102.2 parts of the aqueous polyacrylate solution described under a) as a dispersant, a pH of about 9.2 being established.
  • the mixture is then stirred for a further 30 minutes at 20 ° C.
  • the entire amount of the diazonium salt solution from b) is then added dropwise to the dispersion prepared in this way, which has a pH of 9.2, below the surface at 20 ° C. in the course of 1 hour.
  • the pH is determined by the metered addition of a mixture
  • the pigment dispersions prepared according to Examples 1 to 5 above are purified, desalted and concentrated by means of membrane filtration (ultrafiltration: commercially available polysulfone membrane with a selectivity of 3500 daltons; area: 16 cm 2 ).
  • membrane filtration ultrafiltration: commercially available polysulfone membrane with a selectivity of 3500 daltons; area: 16 cm 2 .
  • the filtration system is connected to an N 2 compressed gas bottle and pressurized with 30 bar. 200 ml of saline solution are eluted per process step, then the system is depressurized and filled with 200 ml of deionized water.
  • the desalination process is monitored by measuring the conductivity of the eluate. Typically, the conductivity of freshly made pigment or
  • Dye dispersions in a range between 5 and 7 mS / cm.
  • the conductivity has dropped to a value of 0.2 mS / cm, ie after approx. If 2000 ml of water are eluted, the desalination is stopped. If necessary, the dispersion can be concentrated by a factor of approx. 4-8 by no longer adding to the ultrafiltrate; the concentration of colorant can thus be increased from 0.4 - 3% to 3 - 25%.
  • Viscosity measurement (dynamic viscosity) The viscosity was determined using a cone-plate viscometer (Roto Visco 1) from Haake (titanium cone: 0 60 mm, 1 °), the dependence of the viscosity on the shear rate in a range between 0 and 700 1 / s was examined. Depending on the pigment and dispersant concentration, the pigment preparations listed in the examples have viscosities between 1 mPas and 50 mPas and thus show excellent flowability. Even during long storage periods there are no or only very slight changes in viscosity, i.e. the dispersions are all very stable.
  • the particle sizes of the preparations were determined using the CHDF method (capillary hydrodynamic fractioning).
  • Pigment dispersions each before and after desalination and concentration, determined. The measurements show that in all cases there are only slight changes in the mean particle sizes. In the course of desalination and
  • the pigment dispersions were first filtered through a 1 ⁇ m filter to remove any coarse particles, e.g. To separate dust particles.
  • the filtered preparations were then optionally diluted with water and mixed with other low molecular weight alcohols and polyols.
  • the composition of the test inks was chosen so that the viscosity was in a range from 1.5 to 5 mPas.
  • small amounts of surfactant can also be added if necessary.
  • the investigations provide additional information on the shape of the ink drops and show irregularities in the drop formation, which are caused, for example, by clogging of individual nozzles.
  • the investigated inks have a very good jet formation behavior, which can be seen from the fact that the individual ink jets are aligned in parallel and leave the nozzles perpendicular to the surface. None of the nozzles are clogged.
  • the jet and drop formation is very regular, with individual drops forming from the ink jets over time, smaller satellite drops are not observed.
  • test images were printed on commercially available normal paper (copy paper) and special paper (premium quality from HP) using a commercially available printer (HP 420).
  • the printouts were assessed visually with regard to the quality and quality of the printed image. It was examined whether the paper was excessively moistened, whether the pigment penetrated the paper or whether it adhered to the surface of the paper. Furthermore, it was examined how exactly fine lines were reproduced, whether the ink ran on the paper, which resulted in low resolution, or whether high-resolution prints could be produced. After longer pauses in printing, the pressure behavior was examined, i.e. whether a good and error-free printout was guaranteed immediately or whether individual nozzle channels were blocked due to drying of the ink, which led to a poor print image.
  • Criteria a) and b) were used to assess the printing behavior and the printing quality of the inks on the basis of the following evaluation scale with the marks from 1 to 6 (see Table 2):
  • the pigment preparations thus meet the requirements of ink-jet printing in terms of the physical and printing properties in an excellent manner and are therefore particularly suitable for applications in ink-jet printing.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

L'invention concerne un procédé permettant de produire des dispersions à fines particules de colorants azo insolubles dans l'eau à peu solubles, qui se caractérise en ce qu'il est prévu de coupler un sel de diazonium apte au couplage, avec un constituant de couplage, en présence d'au moins 45 % en poids, par rapport à la quantité de colorant théoriquement attendue, d'un agent tensioactif.
PCT/EP2002/012599 2001-12-14 2002-11-12 Procede de production de preparations de colorants azo a fines particules pour l'impression par jet d'encre WO2003052000A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10161609A DE10161609A1 (de) 2001-12-14 2001-12-14 Verfahren zur Herstellung feinteiliger Azofarbmittelpräparationen für den Ink-Jet-Druck
DE10161609.0 2001-12-14

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WO2003052000A1 true WO2003052000A1 (fr) 2003-06-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006119847A2 (fr) * 2005-05-06 2006-11-16 Clariant Produkte (Deutschland) Gmbh Préparation pigmentaire à base d'un pigment azoïque
WO2006119846A2 (fr) * 2005-05-06 2006-11-16 Clariant Produkte(Deutschland) Gmbh Pigment azoique a fines particules et procede de realisation associe
CN101525500A (zh) * 2008-03-07 2009-09-09 施乐公司 苯并咪唑酮颜料的纳米尺度颗粒
EP2290012A3 (fr) * 2009-07-24 2011-12-28 Xerox Corporation Composition de particule à pigment nanométrique et son procédé de production
CN105670340A (zh) * 2016-01-14 2016-06-15 上虞市新利化工有限公司 一种c.i.颜料黄180的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050070629A1 (en) * 2003-08-06 2005-03-31 Roberts C. Chad Inkjet ink

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1169063A (fr) * 1955-12-28 1958-12-22 Gen Aniline & Film Corp Procédé de préparation de pigments azoïques
FR2176040A1 (fr) * 1972-03-15 1973-10-26 Ici Ltd
JPS5147179A (en) * 1974-10-18 1976-04-22 Matsui Shikiso Kagaku Kogyosho Senshoku oyobi natsusenhoho
FR2365609A1 (fr) * 1976-09-25 1978-04-21 Bayer Ag Procede de preparation de dispersions aqueuses de colorants azoiques exempts de groupes hydrosolubilisants
GB2014597A (en) * 1978-02-14 1979-08-30 Ici Ltd Continuous Coupling Process
EP0136619A2 (fr) * 1983-09-21 1985-04-10 Ciba-Geigy Ag Procédé de fabrication de préparations de colorants azoiques
US4927466A (en) * 1989-07-07 1990-05-22 Basf Corp. Transparent, high strength organic pigments and process for making same
EP0953615A2 (fr) * 1998-04-30 1999-11-03 Hewlett-Packard Company Procédé d' homogénéisation pour encre d' impression par jet contenant de fines dispersions de pigments

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1169063A (fr) * 1955-12-28 1958-12-22 Gen Aniline & Film Corp Procédé de préparation de pigments azoïques
FR2176040A1 (fr) * 1972-03-15 1973-10-26 Ici Ltd
JPS5147179A (en) * 1974-10-18 1976-04-22 Matsui Shikiso Kagaku Kogyosho Senshoku oyobi natsusenhoho
FR2365609A1 (fr) * 1976-09-25 1978-04-21 Bayer Ag Procede de preparation de dispersions aqueuses de colorants azoiques exempts de groupes hydrosolubilisants
GB2014597A (en) * 1978-02-14 1979-08-30 Ici Ltd Continuous Coupling Process
EP0136619A2 (fr) * 1983-09-21 1985-04-10 Ciba-Geigy Ag Procédé de fabrication de préparations de colorants azoiques
US4927466A (en) * 1989-07-07 1990-05-22 Basf Corp. Transparent, high strength organic pigments and process for making same
EP0953615A2 (fr) * 1998-04-30 1999-11-03 Hewlett-Packard Company Procédé d' homogénéisation pour encre d' impression par jet contenant de fines dispersions de pigments

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 197623, Derwent World Patents Index; Class A23, AN 1976-42941X, XP002231305 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006119847A2 (fr) * 2005-05-06 2006-11-16 Clariant Produkte (Deutschland) Gmbh Préparation pigmentaire à base d'un pigment azoïque
WO2006119846A2 (fr) * 2005-05-06 2006-11-16 Clariant Produkte(Deutschland) Gmbh Pigment azoique a fines particules et procede de realisation associe
WO2006119847A3 (fr) * 2005-05-06 2007-03-01 Clariant Produkte Deutschland Préparation pigmentaire à base d'un pigment azoïque
WO2006119846A3 (fr) * 2005-05-06 2007-03-08 Clariant Produkte Deutschland Pigment azoique a fines particules et procede de realisation associe
JP2008540705A (ja) * 2005-05-06 2008-11-20 クラリアント・プロドゥクテ・（ドイチュラント）・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング 微細なアゾ顔料及びそれの製造方法
US7855041B2 (en) 2005-05-06 2010-12-21 Clariant Produkte (Deutschland) Gmbh Pigment preparation based on an azo pigment
CN101525500A (zh) * 2008-03-07 2009-09-09 施乐公司 苯并咪唑酮颜料的纳米尺度颗粒
EP2110412A3 (fr) * 2008-03-07 2010-11-24 Xerox Corporation Particules de pigments de benzimidazolone de taille nano
KR101539924B1 (ko) * 2008-03-07 2015-07-28 제록스 코포레이션 나노크기의 벤즈이미다졸론 안료 입자
EP2290012A3 (fr) * 2009-07-24 2011-12-28 Xerox Corporation Composition de particule à pigment nanométrique et son procédé de production
CN105670340A (zh) * 2016-01-14 2016-06-15 上虞市新利化工有限公司 一种c.i.颜料黄180的制备方法

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