Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
  • C07D487/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
  • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
• • 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
  • C09B57/00—Other synthetic dyes of known constitution
  • C09B57/004—Diketopyrrolopyrrole dyes
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
• • 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
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
  • C09B67/0034—Mixtures of two or more pigments or dyes of the same type
  • C09B67/0039—Mixtures of diketopyrrolopyrroles

Definitions

• the present invention relates to a pigment composition of compounds of formula (I), (II) and (III) having a novel crystal modification, their preparation and the use of this new product as a pigment.
• EP-A-0 181 290 discloses pigment compositions of diketopyrrolopyrroles (DPPs) which can be prepared by mixed synthesis from two different nitriles A and B from succinic diesters, the molar proportions of the nitriles disclosed in the examples being in the range from 88 to 99.9 mol. % A to 12 to 0.1 mol% B lie.
• DPPs diketopyrrolopyrroles
• EP-A-0 962499 discloses a pigment composition prepared by mixed synthesis of 50 mol% of 3-chloro and 50 mol% of 4-chlorobenzonitrile with succinic diesters in the presence of a crystal growth inhibitor.
• Example 1e discloses a pigment composition prepared by mixed synthesis of 70 mol% of 3-chloro and 30 mol% of 4-chlorobenzonitrile and acid precipitation of the pigment alkali salt.
• the object was to provide a diketopyrrolopyrrole pigment composition with an orange to red color, which has both a high transparency and fineness of the pigment crystals, as well as a high hue purity and brilliance.
• the present invention relates to a mixed crystal of compounds of the formula (I), (II) and (III),
• X chlorine, methyl or nitrile, wherein the molar proportions of the 3-chloro and 4 X-benzonitriles in the sum of 100 mol%.
• X is chlorine.
• mixed crystals also include "solid
• the properties of the mixed crystals differ both from the properties of the individual components, as well as the properties of the physical mixtures of binzelkomponenten.
• the X-ray powder diagrams of the mixed crystals differ from those of the corresponding physical mixtures and from the sum of the powder diagrams of the individual compounds.
• the new mixed-crystal modification is characterized by a different X-ray diffraction pattern from the previously known modifications obtained from mixed syntheses of 3- and 4-X-benzonitriles, namely by a characteristic line at 18.5 (Cu-K ⁇ radiation, 2 theta). Values in degrees, measuring accuracy +/- 0.2 °).
• the mixed crystals of the invention can be obtained in a fineness corresponding to a BET surface area of 90 to 150 m 2 / g, preferably 92 to 130 m 2 / g.
• the present invention also provides a process for the preparation of the mixed crystals according to the invention by reacting succinic diesters with 3-chloro- and 4-X-benzonitrile in the above proportions, in an organic solvent, in the presence of a strong base and at elevated temperature to form one
• Pigmentalkalisalzes subsequent hydrolysis of the pigment alkali metal salt in water and / or alcohol and optionally subsequent Lentelfelfishish.
• the total concentration of the nitriles in the organic solvent is suitably 0.5 to 5 mol / l.
• the molar ratio of the strong base to the succinic diester is suitably 0.1 to 10 moles of base to 1 mole of succinic diester.
• the reaction temperature for the formation of the pigment alkali salt is expediently 60 to 140 ° C., preferably 80 to 120 ° C.
• the succinic diesters to be used may be dialkyl, diaryl or monoalkylmonoaryl esters, it also being possible for the succinic acid dialkyl esters and diaryl esters to be asymmetrical. Preference is given to using symmetrical succinic diesters, in particular symmetrical succinic acid dialkyl esters. Lies a
• Succinic acid diaryl esters or monoaryl monoalkyl esters aryl in particular denotes unsubstituted or by 1, 2 or 3 substituents from the group halogen, such as chlorine, C 1 -C 6 -alkyl, such as methyl, ethyl, isopropyl, tert-butyl or tert-butyl.
• Aryl is preferably unsubstituted phenyl.
• alkyl may be unbranched, branched or cyclic, preferably branched, and preferably 1 to 18, in particular 1 to 12, especially 1 to 8 and particularly preferably 1 to 5 C-atoms contain.
• Alkyl is preferably sec- or tert-alkyl, for example isopropyl, sec-butyl, tert-butyl, tert-amyl, cyclohexyl, heptyl, 2,2-dimethylhexyl, octyl, decyl, dodecyl, tetradecyl or octadecyl ,
• succinic diesters are dimethyl succinate, diethyl ester, dipropyl ester, dibutyl ester, dipentyl ester, dihexyl ester, -diheptyl esters, dioctyl esters, diisopropyl esters, di-sec-butyl esters, di-tert-butyl esters, di-tert-amyl esters, di- [1,1-dimethylbutyl] esters, di- [ 1, 1, 3,3-tetramethylbutyl] ester, di- [1, 1-dimethylpentyl] ester, di- [1-methyl-1-ethyl-butyl] ester, di- [1, 1 diethylpropyl] ester, diphenyl ester, di- [4-methylphenyl] ester, di- [2-methylphenyl] ester, di- [4-chlorophenyl] ester, di- [2,4- dichlorophen
• symmetrical succinic acid dialkyl esters are used, wherein alkyl is branched and contains 3 to 5 carbon atoms.
• the reaction of the succinic diester with the nitrile is carried out in an organic solvent.
• Suitable solvents are, for example, primary, secondary or tertiary alcohols having 1 to 10 C atoms, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, pentanols, such as n-pentanol or 2-methyl-2-butanol, hexanols such as 2-methyl-2-pentanol or 3-methyl-3-pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, octanols such as 2,4 , 4-trimethyl-2-pentanol, cyclohexanol, or glycol
• Diethylene glycol monoethyl ether, butylglycols or methoxybutanol, dipolar aprotic solvents for example acid amides such as dimethylformamide, N, N-dimethylacetamide or N-methylpyrrolidone, urea derivatives such as tetramethylurea, aliphatic or aromatic hydrocarbons such as cyclohexane or benzene or by alkyl, alkoxy, nitro or halogen substituted benzene such as toluene, xylene, ethylbenzene, anisole, nitrobenzene, chlorobenzene, o-dichlorobenzene or 1, 2,4-trichlorobenzene, aromatic N-heterocycles such as pyridine, picoline or quinoline, and hexamethylphosphoric triamide, 1, 3-dimethyl-2 -imidazolidinone, dimethyl sulfoxide or sulfolane.
• Suitable strong bases are, in particular, the alkali metals themselves, such as lithium, Sodium or potassium, or alkali metal amides, such as lithium, sodium or potassium amide, or alkali metal hydrides, such as lithium, sodium or potassium hydride, or alkaline earth or alkali metal alkoxides, in particular of primary, secondary or tertiary aliphatic alcohols having 1 to 10 C
• Suitable strong bases are, in particular, the alkali metals themselves, such as lithium, Sodium or potassium, or alkali metal amides, such as lithium, sodium or potassium amide, or alkali metal hydrides, such as lithium, sodium or potassium hydride, or alkaline earth or alkali metal alkoxides, in particular of primary, secondary or tertiary aliphatic alcohols having 1 to 10 C
• alkali metal alkoxides alkali particularly meaning sodium or potassium
• the alkoxide preferably being derived from a secondary or tertiary alcohol.
• Particularly preferred strong bases are therefore, for example, sodium or potassium isopropylate, sec-butoxide, tert-butylate and tert-amylate.
• the alkali metal alkoxides can also be prepared in situ by reacting the corresponding alcohol with the alkali metal, alkali metal hydride or alkali metal amide.
• Hydrolysis of the pigment alkali salt may be carried out using water or one or more organic, protic solvents as hydrolysis agent.
• Protic solvents are e.g. Alcohols, preferably having 1 to 4 carbon atoms, such as methanol or ethanol, into consideration. It is also possible to use water and alcohol in any combination.
• the hydrolysis can also be carried out in the presence of organic aprotic solvents.
• the hydrolysis can be carried out directly by adding a hydrolysis agent to the reaction suspension, or indirectly, by adding the reaction suspension to the hydrolysis agent.
• the hydrolysis agents water and organic protic solvent can be added and / or presented in any order and also as mixtures. A simultaneous addition of individual components to a template is possible. It may be advantageous to use a buffer during hydrolysis, such as a phosphate, acetate, citric acid or triethanolamine buffer.
• the temperature in hydrolysis may be from -20 0 C to 200 0 C, preferably from -5 to 180 0 C, in particular 0 to 160 0 C, if appropriate, the hydrolysis takes place under pressure.
• Reaction suspension and hydrolysis agents may also have different temperatures.
• the hydrolysis can also be done by means of water vapor.
• the total amount of hydrolysis agent is expediently an at least stoichiometric amount based on base.
• water and / or an organic, protic solvent can be used between 0.5 and 50 parts by weight per 1 part of the resulting pigment.
• the mixed crystals according to the invention can subsequently also be finished without the crystal modification changing.
• the fine particles can grow again, so that depending on the desired application, the finishing conditions are adjusted accordingly.
• the finishing conditions which lead to more opaque particles are known to the person skilled in the art and are described, for example, in WO 02/085 987.
• the procedure is preferably such that the pigment suspension obtained in the hydrolysis of the pigment alkali metal salt for 0.1 to 8 hours, in particular 0.5 to 6 hours, to a temperature of 50 to 150 0 C, in particular 80 to 130 0 C, optionally under pressure , is heated.
• Advantageous may be the presence of surfactants which inhibit crystal growth.
• pigment dispersants can be added at any point in the process, if these do not affect the advantages of the invention. It is also possible to use mixtures of these additives.
• the addition of the additives can be done all at once or in several portions.
• the additives can on be added to any point of the synthesis or the various post-treatments, or after the post-treatments. The most appropriate time must first be determined by preliminary experiments.
• the mixed crystals of the invention can be used in principle for pigmenting all high molecular weight organic materials of natural or synthetic origin, for example of plastics, resins, paints, especially metallic paints, paints, printing inks, electrophotographic toners and developers, electret materials, color filters and inks, especially ink -Jet inks.
• High molecular weight organic materials which can be pigmented with the mixed crystals according to the invention are, for example, cellulose compounds, such as, for example, cellulose ethers and esters, such as ethylcellulose, nitrocellulose, cellulose acetates or cellulose butyrates, natural binders, for example fatty acids, fatty oils, resins and the like
• Conversion products, or synthetic resins such as polycondensates, polyadducts, polymers and copolymers, such as aminoplasts, in particular urea and melamine-formaldehyde resins, alkyd resins, acrylic resins, phenolic resins and phenolic resins, such as novolaks or resols, urea resins, polyvinyls, such as polyvinyl alcohols, polyvinyl acetals, polyvinyl acetates or polyvinyl ethers,
• Polycarbonates such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, poly (meth) acrylates and their copolymers, such as polyacrylic or polyacrylnithle, polyamides, polyesters, polyurethanes, coumarone-indene and hydrocarbon resins, epoxy resins, unsaturated resins (polyesters, acrylates) with the different hardening mechanisms, waxes, aldehyde and ketone resins, rubber, rubber and its derivatives and latices, casein, silicones and silicone resins; individually or in mixtures.
• polyolefins such as polystyrene, polyvinyl chloride, polyethylene or polypropylene
• poly (meth) acrylates and their copolymers such as polyacrylic or polyacrylnithle, polyamides, polyesters, polyurethanes, coumarone-indene and hydrocarbon resins, epoxy resins, unsaturated resins (polyesters,
• the mixed crystals according to the invention are usually used in an amount of from 0.01 to 30% by weight, preferably from 0.1 to 20% by weight.
• the mixed crystals according to the invention are also suitable as colorants in electrophotographic toners and developers, such as, for example, one- or two-component powder toners (also called one- or two-component developers), magnetic toners, liquid toners, polymerization toners and special toners.
• Typical toner binders are polymerization, polyaddition and
• Polycondensation resins such as styrene, styrene acrylate, styrene butadiene, acrylate, polyester, phenolic epoxy resins, polysulfones, polyurethanes, individually or in combination, as well as polyethylene and polypropylene, which may contain other ingredients, such as charge control agents, waxes or flow aids or be modified afterwards with these additions.
• the mixed crystals according to the invention are as colorants in ink jet
• Ink-jet inks generally contain a total of 0.5 to 15 wt .-%, preferably 1, 5 to 8 wt .-%, (calculated dry) one or more of the mixed crystals according to the invention.
• Microemulsion inks are based on organic solvents, water and optionally an additional hydrotropic substance (interface mediator). Microemulsion inks generally contain from 0.5 to 15% by weight, preferably
• Hot-melt inks are usually based on waxes, fatty acids, fatty alcohols or sulfonamides, which are solid at room temperature and liquid when heated, the preferred melting range between about 60 0 C and 140 0 C is about.
• hot-melt ink-jet inks consist essentially of 20 to 90% by weight of wax and 1 to 10% by weight of one or more of the mixed crystals according to the invention.
• 0 to 20 wt .-% of an additional polymer (as a "dye remover"), 0 to 5 wt .-% dispersing aid, 0 to 20 wt .-% viscosity modifier, 0 to 20 wt .-% Piastifizierer, 0 to 10 wt % Of tackiness additive, 0 to 10% by weight of transparency stabilizer (prevents, for example, crystallization of the waxes) and 0 to 2% by weight of antioxidant.
• the mixed crystals according to the invention are colorants for color filters, both for additive and for subtractive color generation, such as in electro-optical systems such as television screens, liquid crystal displays, charge coupled devices, plasma displays or electroluminescent displays, which in turn can be active (twisted nematic) or passive (supertwisted nematic) ferroelectric displays or light-emitting diodes, as well as colorants for electronic inks ("electronic inks" or "e-inks”) or "electronic paper”("e-paper”) suitable.
• electro-optical systems such as television screens, liquid crystal displays, charge coupled devices, plasma displays or electroluminescent displays, which in turn can be active (twisted nematic) or passive (supertwisted nematic) ferroelectric displays or light-emitting diodes, as well as colorants for electronic inks ("electronic inks" or "e-inks”) or "electronic paper”("e-paper”) suitable.
• binders acrylates, acrylic esters, polyimides, polyvinyl alcohols, epoxies, polyesters, melamines, gelatin, caseins
• a stable paste or a pigmented photoresist also has a high pigment purity Requirement.
• the pigmented color filters can also through
• Ink jet printing process or other suitable printing process can be applied.
• red shades of the mixed crystals according to the invention are particularly well suited for the color filter color set red-green-blue (R 1 G 1 B) - These three colors are present as separate color points next to each other, and result from backlit a full-color image.
• Typical colorants for the red color point are pyrrolopyrrole, quinacridone and azo pigments, e.g. Cl. Pigment Red 254, Cl. Pigment Red 209, Cl. pigment
• Color point typically phthalocyanine colorants are used, such.
• the mixed crystal pigment according to the invention by dry mixing with organic or inorganic masses,
• Granules, fibers, powders and other pigments to process mixtures are provided.
• the pigment obtained has a BET surface area of 56 m 2 / g and is characterized in
• the pigment is prepared according to WO 02/085987 A1, Example 1 e from a mixture of 70 mol% of 3-chlorobenzonitrile and 30 mol% of 4-chlorobenzonitrile.
• the pigment obtained has a BET surface area of 87 m 2 / g and is characterized in the X-ray powder diagram by the following characteristic lines:
• Comparative Example 3 (70% 3-chlorobenzonitrile, 30% 4-chlorobenzonitrile, precipitation on water): 21.7 parts of 3-chlorobenzonitrile and 9.3 parts of 4-chlorobenzonitrile are dissolved in 30% sodium amylate (prepared from 9.3 parts of sodium and 143 parts of amyl alcohol) and heated to 100 0 C. 30 parts of diisopropyl succinate are added within two hours. After a further four hours at 100 0 C, the Pigmentalkalisalz suspension is cooled to 80 0 C and added to 60 0 C hot water. The pigment suspension is then heated for conditioning for five hours at 95 0 C, filtered off, washed with methanol and water and dried in a drying oven at 75 0 C. This gives an orange-red pigment.
• the pigment obtained has a BET surface area of 73 m 2 / g and is characterized in the X-ray powder diagram by the following characteristic lines:
• Example 1 (mixed crystal of 80 mol% of 3-chlorobenzonitrile, 20 mol% of 4-chlorobenzonitrile):
• the pigment is prepared analogously to Comparative Example 3, except that 24.8 parts
• the pigment obtained has a BET surface area of 103 m 2 / g and is much finer in particle size than the pigments from Comparative Examples 1 and 3. It is characterized in the X-ray powder diagram by the following characteristic lines:
• the pigment is prepared analogously to Comparative Example 3, except that 25.8 parts of 3-chlorobenzonitrile and 5.2 parts of 4-chlorobenzonitrile are used. This gives an orange-red pigment.
• the pigment obtained has a BET surface area of 98 m 2 / g and is much finer in particle size than the pigments from Comparative Examples 1 and 3. It is characterized in the X-ray powder diagram by the following characteristic lines:
• Example 3 (mixed crystal of 92 mol% of 3-chlorobenzonitrile, 8 mol% of 4-chlorobenzonitrile):
• the pigment is prepared analogously to Comparative Example 3, except that 28.4 parts of 3-chlorobenzonitrile and 2.6 parts of 4-chlorobenzonitrile are used. This gives an orange-red pigment.
• the pigment obtained has a BET surface area of 99 m 2 / g and is much finer in particle size than the pigments from Comparative Examples 1 and 3. It is characterized in the X-ray powder diagram by the following characteristic lines:
• Example 4 (mixed crystal of 83 mol% of 3-chlorobenzonitrile, 17 mol% of 4-methylbenzonitrile):
• the pigment is prepared analogously to Comparative Example 3, except that 25.8 parts of 3-chlorobenzonitrile and 5.2 parts of 4-methylbenzonitrile are used. This gives an orange-red pigment.
• the resulting pigment has a BET surface area of 102 m 2 / g and is much finer in particle size than the pigments of Comparative Examples 1 and 3.
• the characteristic novel line of the inventive crystal modification at 18.5 ° (+/- 0.2) 2 theta is available.
• Example 5 (mixed crystal of 83 mol% of 3-chlorobenzonitrile, 17 mol% of terephthalonitrile):
• the pigment is prepared analogously to Comparative Example 3, except that 25.8 parts of 3-chlorobenzonitrile and 5.2 parts of terephthalonitrile are used. This gives an orange-red pigment.
• the resulting pigment has a BET surface area of 109 m 2 / g and is much finer in particle size than the pigments of Comparative Examples 1 and 3.
• Examples 1 to 5 according to the invention are very much finer crystalline than Comparative Examples 1 to 3.
• the pigments obtained were completely dispersed in a transparent alkyd-melamine stoving lacquer system.
• a whitening varnish was prepared by mixing 6.0 g of the alkyd-melamine solid paint with 20.0 g of a 30% white paint.
• the whitening lacquer obtained was applied together with the sample to be compared side by side on a white card and baked after 30 min air drying for 30 min at 140 0 C.
• the color intensity and its measurement is defined in accordance with DIN EN ISO 787-26.
• the color strengths, chroma (color purity) and transparency of the pigments prepared in the above examples are given in the table below.
• Comparative Examples 1, 2 and 3 are much cloudier ( ⁇ C ⁇ -1, 0) than Examples 1 to 3 according to the invention. Comparative Examples 1 and 3 are also much more opaque than Examples 1 to 3 according to the invention.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Paints Or Removers (AREA)
• Developing Agents For Electrophotography (AREA)
• Nitrogen Condensed Heterocyclic Rings (AREA)

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• 2007
  • 2007-02-19 DE DE102007008140A patent/DE102007008140A1/de not_active Withdrawn
• 2008
  • 2008-01-17 EP EP08707072A patent/EP2121695A1/de not_active Withdrawn
  • 2008-01-17 KR KR20097017164A patent/KR101488033B1/ko active IP Right Grant
  • 2008-01-17 CN CN2008800014666A patent/CN101578286B/zh not_active Expired - Fee Related
  • 2008-01-17 WO PCT/EP2008/000306 patent/WO2008101570A1/de active Application Filing
  • 2008-01-17 US US12/526,922 patent/US8318052B2/en active Active
  • 2008-01-17 JP JP2009549785A patent/JP5235902B2/ja active Active

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