TW200902641A - Pigment preparations based on diketopyrrolopyrroles - Google Patents

Abstract

The invention relates to a pigment preparation comprising C. I. Pigment Red 254 having an average particle size of 20 to 100 nm and also a pigment dispersant of the formula (II) in which Q1 is a radical of an organic pigment from the group of C. I. Pigment Red 264 and C. I. Pigment Violet 19.

Description

</ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; TECHNICAL FIELD OF THE INVENTION The present invention relates to novel pigment preparations comprising C.I. Pigment Red 254 (as a base pigment) and certain anionic pigment dispersants. The pigment preparation is a combination of a primer pigment and a so-called pigment dispersant, which is a pigment substituted with a group having a specific activity. Pigment dispersants are added to the pigment to promote dispersion in the application medium (especially paints and inks, including printing inks) and to improve the rheology and coloring properties of the pigment. This approach may result in increased color intensity, transparency, and gloss in a variety of applications. The color former is made of an extremely fine pigment to largely eliminate particle scattering which causes a decrease in the contrast ratio. [Prior Art] WO 〇 1 /042 1 5 discloses a fine diketopyrrolopyrrole pigment, C · I · Pigment Red 2 5 4 ( I ), 200902641

(1) It is characterized by an extremely narrow particle size distribution as well as high crystallinity and specific absorption characteristics. Such C·I·Pigment Red 2 5 4 can be obtained by first stirring a crude pigment with an inorganic salt under a drying condition of at least 80 ° C, and kneading the product with an inorganic salt in the presence of an organic solvent. Based on this conventional method, commercial products can be made and recommended for applications where transparency is desired. However, these pigments do not fully meet all the requirements of this technology. In particular, it addresses the need for transparency in terms of 'dispersibility and rheology. EP-A1-1 104 789 discloses dispersants based on pigments such as diketopyrrolopyrrole or quinacridone. SUMMARY OF THE INVENTION The object of the present invention is to provide a pigment preparation comprising CI Pigment Red 2 54 as a base pigment. The pigment preparation exhibits high color strength, low viscosity, and has a very low color tone with the CI Pigment Red 254 base pigment. Deviation, and it is especially suitable for color filter applications. It has been found that a pigment preparation having a defined particle size of C I. Pigment Red 254 and a pigment dispersant defined below as a substrate can achieve this purpose, although 200902641 is based on the color of individual compounds, and it is expected that the color deviation will be large. More. The present invention provides a pigment preparation comprising C.I. Pigment Red 254 having an average particle size d5Q of 20 to 100 nm and a pigment dispersant of the formula (n)

Wherein Q is a group of organic pigments derived from C · I · Pigment Red 2 6 4 and c · I. Pigment Vio 19; s is a number from 1 to 5; N is a number from 〇 to 4; the sum of s and η 1 to 5;

Rl is a divalent branched or unbranched, saturated or unsaturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, or a c5-c7 stretching ring, or having 1, 2 or 3 (better 1 or 2) an aromatic ring of a divalent aryl group which may be fused or linked by a bond (for example, phenyl, biphenyl or naphthyl) or having 1, 2 or 3 a divalent heterocyclic group containing 1, 2, 3 or 4 hetero atoms selected from 0, N and S or a combination thereof; the aforementioned hydrocarbon, ring-based, aryl and heteroaryl groups may be passed through 1, 2 , 3 or 4 substituents substituted for the substituent selected from OH, CN, F, Cl, Br, 200902641 N02, CF3, Ci-Ce alkoxy, S-Ci-Ce alkyl, NHCONH2, NHC (NH NH2, NHCO-Ci-Ce alkyl, Κ6 alkyl, COOR20, CONR20R21, NR20R21, S03R20, COCTE+, S03-E+ or S O2-NR20R21, R20 and R21 are the same or different and are hydrogen, phenyl or CkQ alkane R2 is hydrogen, R1 or 1^-(3001+; E+, G + is the equivalent of the metal cation Mm + of the main group 1 to 5 of the periodic table or the transition group of the 1 or 2 or 4 to 8 Mm + / m,m is the number 1, 2 or 3 and p is the number 1, 2 or 3, for example, Li1+, Na1+, K1+ Mg2+, Ca2+, Sr2+, Ba2+, Mn2+, Cu2+, Ni2+, Co2+, Zn2+, Fe2+, Al3+, Cr3 + or Fe3+; or an unsubstituted or substituted ammonium ion. When E + or G + is an ammonium ion, The following are applicable: (i) N + R9R10R1 *R12 &gt; The substituents R9, R1G, R11 and R12 are each independently a hydrogen atom, a CrCw alkyl group, a C2-C3Q alkenyl group, a C5-C3Q cycloalkyl group, a phenyl group. (Ci-Cs)alkyl-phenyl, alkylene-phenyl, such as benzyl, or (poly)alkyloxy of the formula -[CH(R8Q)-CH(R8Q)-0]kH, Wherein k is a number from 1 to 30, and two R815 groups are each independently hydrogen, Ci-Q alkyl, or a combination thereof if k&gt;1; and wherein R9, R1(), R11 and/or R12 represent Alkyl, alkenyl, -8- 200902641 ring-based, phenyl or alkylphenyl may be substituted by an amine group, a hydroxyl group and/or a carboxyl group; or the substituents R9 and R1Q may form a five member together with a fourth-order N atom Up to seven members of the saturated ring system, if necessary, further containing heteroatoms from hydrazine, S and N, such as pyrrolidone, imidazolium, hexamethylenemethylimine, piperidine, piperazine or morpholine; Substituent R9, R 1() and R11 together with a quaternary N atom may form a five to seven member aromatic ring system which, if desired, further contains heteroatoms from hydrazine, S and N, and if necessary, additional rings are thickened To the other, such as pyrrole, imidazole, pyridine, picoline, pyrazine, quinoline or isoquinoline type; or (ii) the money ion of formula (la)

Wherein R 15 , R 16 , R 17 and R 18 are each independently hydrogen or a (poly) alkoxy group of the formula _[CH(R8t)) -CH(R8Q) 〇]kH wherein k is a number from 1 to 30, and The two R8C&gt; groups are independently of each other hydrogen, C1-C4, or, if k&lt;1, the combination 'q is a number from 1 to 10, preferably 1, 2, 3, 4 or 5; 9- 200902641 P is a number from 1 to 5, where P&lt;q+1; T is a branched or unbranched C2-C6 extension base; or 1 of which T can also be branched or unbranched c2 -c6 stretched out the combination. s = 1 to 4, n = 0 to 2, and the sum of s and η is 1 to 4 (II) Pigment dispersants are of particular interest. In particular, the dispersant of formula (II) wherein s 3, η = 0·2 to 1.5 and the sum of s and η is 1 to 3 is of interest. Furthermore, it is particularly interesting to find that Ci-Cio (especially ethyl, propyl or butyl) or branched phenyl (II) pigment dispersant is one of branched or unbranched. By. Further, when E + and G + are the pigment dispersing agents of the formula (II) which are equivalent to the measurement of the equivalent of Ca 2+, Sr 2+ , Ba 2+ or Al 3 + , it is particularly edious. The pigment dispersant of the formula (II) is itself a conventional compound and is prepared by a conventional method, for example, in accordance with EP-B 1 - 1 362 08 1 . In the pigment preparation of the present invention, the weight of the 'C · I · Pigment Red 2 5 4 - Paired Pigment Dispersant is preferably between (9 9 · 9 : 0.1 ) and ( 2 0 ) to 9 9 : 1 ) and (8 3 : 1 7 ) are more particularly between (97 : 3 ) and ( 85 : 15 ), and (9 5 : 5 ) and ( 8 7 : 1 3 ) is especially good. For the mixture of the components C.I. Pigment Red 2 54 and the pigment dispersant B of the present invention, the deviation of Δ 各 in each case is expected to be greater than 3. 〇. Chromaticity (C) is a color that describes the color at a particular brightness. If q&gt; is based on formula = 1 to pigment 3 alkyl oxime, formula I chemistry g interest f by (II) : 80 : ί good, between 乂Propose and △ C scoop coloring - -10-200902641 parameters; AC describes the difference between the color of the two colors. Similarly, ΔH describes the difference in hue between the two colors in comparison. However, it is discernible that it has been found to have a 1/3 standard color depth in the alkyd/melamine resin varnish system using the pigment preparation of the invention according to DIN EN ISO 787-26, and the corresponding pure CI pigment. The hue of red 254 and the same particle size is preferably Δ Η (according to CIELAB) of not more than 2.0, particularly not more than 1.5, and more preferably not more than 1.0. Preferably, Δ C (according to CIELAB) is not more than 2.0, particularly not more than 1.5, and more preferably not more than 1.0. The pigment preparation of the present invention is preferably high in crystallinity, characterized in that in the X-ray powder diffraction pattern irradiated with C u · 〇 〇: the main peak width of the half-height height is 0.2 to 0·7 ° 2 Θ, in particular It is 0.3 to 0.510. The pigment preparation of the present invention comprises a base pigment having an average particle size d5G of from 20 to 1 nm, and d5G is preferably from 30 to 80 nm. The particle size distribution of C.I. Pigment Red 254 is preferably close to a Gaussian distribution, wherein the standard deviation σ is preferably less than 40 nm, more preferably less than 30 nm. In general, this standard deviation is between 5 and 40 nm and is preferably between 1 and 30 nm. The pigment preparation of the present invention unexpectedly has an extremely low viscosity, and its viscosity measured at 20 ° C by a cone-and-plate type viscometer (e.g., RS75 of Haake) is preferably from 3 to 50 mPa·s. In addition to the diketopyrrolopyrrole pigment and the pigment dispersant, the pigment preparation of the present invention may further contain conventional adjuvants or additives, for example, surfactants, dispersants, dips, standardizers, resins, waxes, and deodorants. -11 - 200902641 Agent, dusting agent, extender, antistatic agent, preservative, drying retarder, wetting agent, antioxidant, UV absorber and light stabilizer, based on the total weight of the pigment preparation, with a content of 0.1 It is preferably from 0% by weight to 10% by weight, particularly from 0.5% by weight to 5% by weight. Suitable interfacial agents include anionic or anionic active, cationic or cationic active, and nonionic or zwitterionic materials, or mixtures of such agents. Examples of suitable anionic materials include fatty acid taurate, fatty acid N-methyl taurate, fatty acid 2-hydroxyethanesulfonate, alkylphenyl sulfonate (example of which is dodecylbenzenesulfonic acid) ), alkyl naphthalene sulfonate, alkyl phenol polyglycol ether sulfate, fatty alcohol polyglycol ether sulfate, fatty acid guanamine polyglycol ether sulfate, alkyl sulfonate amber phthalate, sulfonate Acid alkenyl succinic acid monoester, fatty alcohol polyglycol ether sulfonic acid sulfosuccinate, alkane sulfonate, fatty acid glutarate, alkyl thiosuccinate, fatty acid sarcosine Fatty acids, such as palmitic acid, stearic acid and oleic acid; salts and soaps of these anionic substances, such as alkali metal salts of fatty acids, naphthoic acid, resin acids and rosin acids, such as alkali-soluble resins, rosin-modified cis a -butenediate resin, and a condensation product based on cyanuric acid chloride, taurine, N,N'-diethylaminopropylamine and p-phenylenediamine. Preferred are resin soaps, i.e., alkali metal salts of resin acids. Examples of suitable cationic materials include quaternary ammonium salts, fatty amine oxyalkylates, polyoxyalkylene amines, oxyalkylated polyamines, fatty amine polyglycol ethers, primary, secondary or tertiary amines, Examples are alkylamines, cycloalkylamines or cyclized alkylamines, in particular fatty amines, diamines and polyamines derived from fatty amines or lipids-12-200902641, and the oxyalkylates of the amines, An imidazoline or polyamine based compound or resin derived from a fatty acid, an imidazoline having an amine index between 1 Å and 800 mg KOH per gram of polyamine amide or a polyamine compound, and these a salt of a cationic substance such as acetate or chloride. Examples of suitable nonionic and zwitterionic materials include fatty amine carboxyglycolate, amine oxides, fatty alcohol polyglycol ethers, fatty acid polyglycol esters, betaines (eg fatty acid guanamine N-propyl betaine). , phosphates of aliphatic and aromatic alcohols, fatty alcohol or fatty alcohol polyglycol ethers, fatty acid decyl ethoxylates, fatty alcohol-alkylene oxide adducts, and alkyl phenyl polyglycol ethers. The non-pigment type dispersant refers to a substance which is not structurally derived from an organic pigment. It is added in the form of a dispersant during the actual preparation of the pigment, but is usually also added when the pigment is incorporated into the application medium to be colored: for example, by dispersing the pigment to the corresponding binder during the production of the color filter. in. They may be polymeric substances, examples being polyolefins, polyesters, polyethers, polyfluorene's polyimines, polyacrylates, polyisocyanates, block copolymers thereof, corresponding, copolymers of monomers, or A few different types of monomers have been modified to one of the polymers. These polymeric materials carry polar chelating groups such as hydroxyl, amine, imido and ammonium groups, carboxylic acid and carboxylate groups, sulfonic acid and sulfonate groups or phosphonic acid and phosphonate groups, Further, it may be modified by an aromatic non-pigment type substance. The non-pigment type dispersant may also be an aromatic substance which is chemically modified with a functional group and is not derived from an organic pigment. Such non-pigment type dispersing agents are known to those skilled in the art and are commercially available in some cases (e.g.,

Solsperse®, Avecia; Disperbyk®, Byk-Chemie; Efka®, -13- 200902641

Efka). Although any of the other substances described may be used in principle, but several types are also listed below, examples of which are isocyanates and alcohols, diols or polyols, amino or diamines or polyamines. a condensation product, a polymer of a hydroxy residual acid, a copolymer of a dilute hydrocarbon monomer or an ethyl cyano monomer with an ethylenically unsaturated carboxylic acid and a carboxylic acid ester, and an urethane-containing polymerization of an ethylenically unsaturated monomer , urethane-modified polyacetate, condensation product based on guanidine cyanurate halide, polymer containing nitroxide, polyester decylamine, modified polyamine, modified a polyacrylic acid polymer, a dispersant comprising a polyester-like and acrylic acid-like polymer having a comb-like structure, a phosphate ester, a triamide-derived polymer, a modified polyether, or derived from an aromatic non- A dispersant for pigment-based substances. In many cases, these parent structures are further modified by, for example, chemical reaction with additional species bearing functional groups or by salt formation. The pigment preparation of the present invention can be used as a preferred aqueous cake or aqueous gas granule, but it usually comprises a powdery essentially solid system. The invention also provides a process for the preparation of a pigment preparation of the invention comprising admixing C.I. Pigment Red 254 with a pigment dispersant of formula (II) prior to or during the operation of kneading, wet milling, dry milling or processing. For example, the dry component in the form of granules or powder may be mixed before or after any honing; one component may be added to the other component in aqueous or dry form. For example, the components are mixed in the form of a filter cake containing water. Mixing can be accomplished by, for example, dry, wet honing, or by kneading, or in suspension, or by a combination of these methods. The honing can be carried out by adding water, a solvent, an acid or a honing aid such as a salt. -14- 200902641 Mixing can also be accomplished by adding a pigment dispersant during the operation of preparing Cd•Pigment Red 254. This pigment dispersant is added to C.I. Pigment Red 254' but 'it is preferably formed after c.I. Pigment Red 254 is chemically formed' and is added before or during the formation of fine particles. A particularly preferred pigment dispersant is added to the diketopyrrolopyrrole pigment during dry or wet milling operations. The fine-grained crystalline pigment preparation formed during honing can be post-treated in, for example, water and/or solvent and generally at elevated temperatures (eg, up to 200 it) and elevated pressure (if needed) (generally referred to as For the final processing). This pigment dispersant can also be added after dry or wet milling, but before or during the final processing. This pigment dispersant can of course also be added in several portions. The aqueous gas pigment preparation can be dried by conventional drying means, such as drying ovens, bucket wheel dryers, drum dryers, contact dryers, particularly rotary flash dryers and spray dryers. The pigment preparation of the present invention is distinguished by its excellent coloring and rheological properties, particularly high flocculation stability, easy dispersibility, good rheology, high color strength, transparency and saturation (chromaticity). They are easily dispersed in a wide range of application media with a high degree of fineness. This pigment dispersion exhibits excellent rheology even when the paint or printing ink concentrate is highly pigmented. Other properties are also extremely good, such as gloss, topcoat fastness, solvent fastness, alkali and acid fastness, light and weather fastness, and high hue purity. Furthermore, the pigment preparations of the present invention can be used to obtain a reddish hue, which is required for color filter applications. In this application, they provide a high contrast and also meet other needs in the range of use of color filters, such as high temperature stability or steep and narrow absorption bands. They can be prepared with high purity and low -15-200902641 sub-content. The pigment preparations of the invention can in principle be used for the coloring of all high molecular weight organic materials of natural or synthetic origin, such as plastics, resins, varnishes, lacquers, in particular metal varnishes, electrophotographic toners and developers. , electret materials, color filters and inks, including printing inks. High molecular weight organic materials which can be colored by the pigment preparation of the present invention are, for example, 'cellulose compounds (for example, cellulose ethers and cellulose esters such as ethyl cellulose, nitrocellulose, cellulose acetate or cellulose). Butyrate), natural binders (for example, fatty acids, fatty oils), resins and conversion products thereof or synthetic resins, for example, polycondensates, polyadducts, addition polymers and copolymers, for example, amine resins (especially urea and melamine formaldehyde resins), alkyd resins, acrylic resins, phenoplasts and phenolic resins (such as novolacs or soluble novolacs), urea resins, polyvinyl compounds (for example, polyethylene) Alcohol, polyvinyl acetal, polyvinyl acetate or polyvinyl ether), polycarbonate, polyolefin (eg polystyrene, polyvinyl chloride, polyethylene or polypropylene), poly(meth)acrylic acid Esters and copolymers thereof (such as polyacrylate or polypropylene), polyamides, polyesters, polyurethanes, coumarone-oxime and hydrocarbon resins, epoxy resins, with or Unsaturated synthetic resins (polyesters, acrylates), waxes, aldehyde and ketone resins, gum, rubber and latex, and derivatives thereof, casein, silicone and silicone ketone ketone resin curing mechanism; individual compound or a mixture of patterns. It does not matter whether the aforementioned high molecular weight organic compound exists in the form of a plastic or a melt or a spinning solution, a dispersion, a varnish, a lacquer or a printing ink of -16-200902641. It has proven advantageous to use the pigment preparation of the present invention in the form of a blend or in the form of a refined product or dispersion, depending on the intended use. It is also possible to prepare this pigment preparation only when it is incorporated into a high molecular weight organic medium. Thus, the present invention also provides a high molecular weight organic material comprising a pigmented effective amount of the pigment preparation of the present invention. The pigment preparation of the present invention is usually used in an amount of from 1% to 3% by weight, preferably from 0.1% to 20% by weight, based on the mass of the organic material to be colored. Higher colorant concentrations can also be used for color filter applications. The pigment preparation of the present invention is also suitable as a color former in an electronic developer and developer, for example, one or two component powder toner (also referred to as one or two component developer), magnetic toner, liquid color Agents, coloring agents and special colorants. Typical toner binders are addition polymer resins, polyaddition resins and polycondensation resins such as styrene, styrene-propionate, styrene-butadiene, propionate, polyester, hydrazine An individual or a combination of an epoxy resin, a polyfluorene or a polyurethane, or a polyethylene and a polypropylene. It may also include other components such as a charge control agent, a wax or a flow aid. 'Or you can subsequently upgrade these ingredients. The pigment preparations of the invention are also suitable as color formers for powders and powder coatings, in particular triboelectric or electrosprayable powder coatings, for coating materials such as metals, wood, plastics, glass, ceramics, concrete, fabrics, The surface of an object made of paper or rubber. Further, the pigment preparation of the present invention is suitable as a coloring agent in inkjet inks for aqueous and non-aqueous substrates, and is also suitable as a coloring agent for water in accordance with the hot melt method of the ink -17-200902641. The inkjet ink usually contains a total of from 0.5 to 15% by weight (on a dry basis) of the pigment preparation of the present invention' and is preferably from 1.5 to 8% by weight. Microemulsion inks are based on organic solvents, water, and, where appropriate, additional solubilizers (interfacial media). The microemulsion ink usually contains 0.5% to 15% by weight (preferably 10.5% to 8% by weight) of the pigment preparation of the present invention, 5% to 99% by weight of water and 〇. 5 % to 9 4.5 by weight % organic solvent and / or solubilized compound. The "solvent-based" inkjet ink preferably contains from 0.5% to 15% by weight of the pigment preparation of the present invention, from 85% to 99.5% by weight of the organic solvent and/or solubilizing compound. Hot melt inks are typically based on waxes, fatty acids, fatty alcohols or sulfoguanamines which are solid at room temperature and liquefied upon heating, with a preferred range of melting between about 60 ° C and about 140 ° C. The hot melt inkjet ink consists essentially of, for example, from 20% to 90% by weight of wax and from 1% to 10% by weight of the pigment preparation of the present invention. They may further comprise from 20% by weight of additional polymer (as "dye-dissolving agent"), from 5% to 5% by weight of dispersing aid, from 0 to 20% by weight of viscosity-modifying agent '0 to 20% by weight of plastic A chemical agent, 0 to 10% by weight of an adhesion additive, 0 to 10% by weight of a transparent stabilizer (which prevents crystallization such as wax), and 0 to 2% by weight of an antioxidant. In particular, the pigment preparation of the present invention is also suitable as a color former for coloring and subtractive color filters, such as photovoltaic systems, such as television screens, LCDs (liquid crystal displays), and charge coupled devices. , plasma display or electroluminescent display (can be active (twisted nematic) or passive (super twisted nematic) ferroelectric display or light emitting diode), and it can also be used as electronic ink (or e-ink) or E-paper (e-paper) coloring -18- 200902641 agent. In the manufacture of color filters (reflective and transmissive color filters), the pigment is in paste form or mixed with a suitable binder (acrylate, acrylate, polyimine, polyvinyl alcohol, epoxide, poly Color-blocking photoresist in ester, melamine, gelatin, casein) is applied to each LCD component (for example, TFT-LCD = thin film transistor liquid crystal display or (S) TN-LCD = (super) twisted nematic L·CD ). In addition to high thermal stability, high pigment purity is a prerequisite for obtaining a stable paste and/or a colored photoresist. In addition, the color smear can also be applied by ink jet printing or other suitable printing methods. The red color of the pigment preparation of the present invention is particularly suitable for the red-green-blue (R, G, B) color filter color set. These three colors are arranged in separate color points and are available in full color when backlit. Typical colorants for red dots are pyrrolopyrrole, quinophthalone and azo pigments, for example C _ I. Pigment Red 2 5 4, C · I. Pigment Red 2 0 9 , C · I. Pigment Red 1 7 5 and C · I. Pigment Orange 3 8, individual pigments or mixed pigments. For green dots, it is usually a phthalocyanine colorant such as C.I. Pigment Green 36 and C.I. Pigment Green 7. Individual color points can also be blended with other colors for background if desired. For red and green tones, it is preferably blended with yellow, such as CI Pigment Yellow 138, 139, 150, 151, 180 and 213°. [Embodiment] In the following examples, parts and percentages are by weight. Unless otherwise stated. -19- 200902641 Example 1: CI Pigment Red 254 Bead-milled in the presence of 10% DPP-based pigment dispersant 70 parts of PR254, 1.4 parts of a commercially available flow improver based on naphthalenesulfonic acid, 8 00 parts of zirconia beads (〇.4-〇·6 mm), 600 parts of water and 7 parts of the pigment dispersant of the formula (V) (which is made in the same manner as in Example 1 of eP-Β卜 1 362 081) a mixture of

Honing in the Drais® Advantis V3 Honing Machine. The duration of honing is equivalent to 5 to 6 theoretical grinding passes. The millbase was separated from the beads and filtered, and the filter cake was heated to reflux with a mixture of 1:1 water and isobutanol at pH 2 for 2 hours. After steam distillation, the mixture was filtered and the solid product was washed with salt-free water, dried under reduced pressure, and finally honed to a powder. Finally, a red pigment preparation having an average particle size d5G of 40 nm (TEM) was obtained. Example 2: CI Pigment Red 254 and Bead Mill with 10% Pigment Dispersant before Solvent Treatment - 200902641 90 parts of PR254, 1.8 parts of a commercially available flow improver based on naphthalenesulfonic acid and 800 parts of water The mixture formed a homogenous paste and was honed in a Drais® Adv ant is V3 honing machine in the presence of 800 parts of zirconia beads (0.4-0.6 mm). The duration of honing is equivalent to 5 to 6 theoretical honing operations. 740 parts of a 10% honing suspension was blended with 7.4 parts of pigment dispersant (V) and isobutanol to give a 1:1 mixture of isobutanol and water. The suspension was heated under reflux at a pH of 2 for 2 hours; after isobutyl alcohol was separated by steam distillation, the solid product was washed with anhydrous water, dried under reduced pressure, and finally honed to a powder. Finally, a red pigment preparation having an average particle size d5G of 48 nm (TEM) was obtained. Example 3: Bead milling of C.I. Pigment Red 254 in the presence of 5% pigment dispersant The same procedure as in Example 1 was followed, but only 3.5 parts instead of 7 parts of the pigment dispersant of formula (V) were used. This produced a red pigment preparation having an average particle size d5C of 53 nm (T E Μ ). Example 4: C.I. Pigment Red 254 Bead Mill in the presence of 1% % Pigment Dispersant Follow the same procedure as in Example 1, but using the pigment dispersant of formula (VI), -21 - 200902641

S-N-(CH2)r〇〇〇·

π approx. 0.3 This gave a red pigment preparation having an average particle size d5 &lt; J of 39 nm (ΤΕΜ). Example 5: CI Pigment Red 254 and a bead mill added with 1% by weight of pigment dispersant before solvent treatment followed the same procedure as in Example 2, but using the pigment dispersant of formula (VI), the average particle size d5〇 was obtained. 46 nanometer (ΤΕΜ) red pigment preparation. Example 6: Be. Milling of C.I. Pigment Red 254 in the presence of 5% Pigment Dispersant The same procedure as in Example 4 was followed, but only 3 · 5 parts instead of 7 parts of the pigment dispersant of formula (VI) was used. This produced a red pigment preparation having an average particle size d5Q of 41 nm (TEM). Example 7: Bead milling of C.I. Pigment Red 254 in the presence of 10% pigment dispersant Follow the same procedure as in Example 1, but using the pigment dispersant of formula (VII), -22-200902641

This produced a red pigment preparation having an average particle size d5 〇 of 37 nm (TEM). Example 8: CI Pigment Red 254 and bead milling with 10% pigment dispersant before solvent treatment followed the same procedure as in Example 2, but using the pigment dispersant of formula (VII), which gave an average particle size d5G of 47 Nai Rice (ΤΕΜ) red pigment preparation. Example 9: C. I. Pigment Red 2 5 4 Bead milling in the presence of 5% pigment dispersant followed the same procedure as in Example 7, but using only 35 parts instead of 7 parts of the pigment dispersant of formula (νπ) . This produced a red pigment preparation having an average particle size of 37 nm (T E Μ ). Example 1 0: C · I. Pigment Red 2 5 4 in η. The bead mill in the presence of the dispersant was followed by the interphase _~' in Example 1 but using the -23-200902641 dispersant of the formula (VIII), which gave an average particle size d5G of 51 nm ( ΤΕΜ ) Red pigment preparation.

Example 1 1 : CI Pigment Red 25 4 and bead milling with 10% pigment dispersant before solvent treatment followed the same procedure as in Example 2, but using the pigment dispersant of formula (VIII), which gave an average particle size dw of 62 nanometer (TEM) red pigment preparation. Example 1 2: C · I · Pigment Red 2 5 4 Bead milling in the presence of 5% pigment dispersant followed the same procedure as in Example 1 ,, but using only 3 to 75 parts instead of 7 parts of the pigment of formula (VIII) Dispersant. This produced a red pigment preparation having an average particle size d50 of 54 nm (TEM). Example 13. Bead milling of CI Pigment Red 254 in the presence of 10% pigment dispersant followed the same procedure as in Example 7, but using 5.6 parts of a commercially available styrene acrylate resin (M &gt; 15,000) sodium salt 25 % aqueous solution, instead of 1 · 4 parts of a mobile flow improver based on neat acid. This produced a red pigment preparation having an average particle size dSQ of 43 nm (TEM). -24- 200902641 Example 1 4: C · I. Pigment Red 2 5 4 Bead milling in the presence of 5% pigment dispersant followed the same procedure as in Example 13 but using only 3.5 parts instead of 7 parts A pigment dispersant of the formula (V111). This produced a red pigment preparation having an average particle size d 5 0 of 41 nm (TEM). Comparative Example A: Bead milling of CI Pigment Red 2 54 in the absence of a pigment-free dispersant. A homogeneous mixture of 90 parts of PR254, 1.8 parts of a commercially available flow improver based on naphthalenesulfonic acid and 800 parts of water was formed. The paste was honed with a Drais® Advantis V3 honing machine in the presence of 8 parts of zirconia beads (0.4-0.6 mm). The duration of honing is equivalent to 5 to 6 theoretical honing strokes. The honing suspension is blended with isobutanol to give a 1:1 mixture of isobutanol and water. The suspension was heated under reflux at a pH of 2 for 2 hours; after isobutyl alcohol was separated by steam distillation, the solid product was washed with water to a salt-free state, dried under reduced pressure, and then pulverized to a powder. Finally, a red pigment preparation having an average particle size d5 〇 of 102 nm (TEM) was obtained. Particle size distribution of the sample: To obtain a particle size distribution, a series of electron micrographs were used. The main particles are visually recognized. The area of each major particle is determined by a chart. The diameter of the circle of equal area is calculated from this area. The frequency distribution of the calculated phase diameters is determined, and the frequencies are converted into volume fractions and expressed in particle size distribution. The standard deviation is an indicator of the distribution width. The smaller the standard deviation, the narrower the particle size distribution. -25- 200902641 Table 1: Particle size distribution and standard deviation sample d50 [nano] standard deviation σ [nano] Example 1 40 16 Example 2 48 24 Example 3 53 15 Example 4 39 15 Example 5 46 23 Example 6 41 18 Example 7 37 18 Example 8 47 21 Example 9 37 15 Example 10 51 19 Example 11 62 27 Example 12 54 24 Example 13 43 15 Example 14 41 14 Comparative Example A 102 42 Crystallinity of the sample: 値 finger at half height The width reflected in the half-peak height of the largest peak (half the maximum 値) in each case (at 2 8 °). The lanthanide at the half-height of the sample is measured with a STOE/β diffractometer (Cu-Kq; ; U = 40 kV, 1 = 40 mA) (slit: main side / vertical 2 x 8 mm, primary side / Level 1.0 mm, secondary side 〇 · 5 鼋 m). The sample holder used was a standard steel support. The measurement time is suitable for the desired statistical reliability. The total observation measurement angle range is 2-3〇. The step width is 0.02. The time is 3 seconds. The range of angles measured in the characteristic range is 2 3 - 3 0. The step width is 〇 · 〇 2. The time is 6 seconds. The X-rays were monochromated by a graphite secondary singlet and were measured with a 260-200902641 scintillation rf* for continuous sample rotation. For the purpose of the evaluation, the profile fit is 20=23_3〇 for the second measurement. The entire angular range is implemented (adjustment function: Lorentz2 (4 reflections)) Table 2: 値Γ2Θ] (main peak) at half height of the crystal sample Example 1 0.36 Example 2 0.41 Example 3 0.47 Example 4 0.35 Example 5 .. 0.39 Example 6 _ 0.41 Example 7 _ 0.45 _ Example 8 0.48 Example 9 0.41 Example 10 0.38 Example 11 0.42 Example 12 0.43 Example 13 0.32 Example 14 — 0.37 Viscosity of the pigment paste for color filter applications: 1 gram The pigment or pigment preparation from the above examples was suspended in 73 g of PGMEA (propylene glycol monomethyl ether acetate), and 17 g of a commercially available high molecular weight block copolymer and 25 g of zirconia beads (〇.3). Millimeter) blended and dispersed in Paintshaker Disperse DAS 200 (available from Lau GmbH) for 3 hours. The viscosity of the pigment paste was measured at 20 ° C using a Haake RS75 cone-plate viscometer. -27- 200902641 Table 3: Viscosity Sample Viscosity [mPa-s] Example 1 28 Example 2 31 Example 3 24 Example 4 19 Example 5 24 Example 6 15 Example 7 11 Example 8 40 Example 9 9 Example 10 15 Example 11 19 Example 12 8 Example 13 12 Example 14 17 Comparative Example A 96 The aforementioned pigment preparation was applied to a glass plate (SCHOTT, laser cut, 10 x 10 cm) using a spin coater (POLOS Wafer Spinner). Because of its low viscosity, it is bright and highly transparent red, with a low film thickness (500 to 1300 nm) and excellent contrast (TSUBOSAKA ELECTRIC CO., LTD, Model CT-1), with no additives The sample is only slightly different in hue. The pigment preparations of Examples 1 to 4 are highly suitable for color filter applications because of their high contrast. Application examples of transparent drying varnish: In order to determine the color strength of the pigment mixture, the chromaticity △ (: and the color tone -28- 200902641 △ Η 'The pigment obtained is completely dispersed in the transparent alkyd-melamine drying varnish system Medium's obtained multi-tone varnish. Next, a white reducing varnish was prepared by mixing 6.0 g of alkyd-melamine multi-tone varnish and 20.0 g of 30% white varnish. The resulting white reducing varnish was applied along the comparative sample. On a white card, air-dried for 30 minutes and baked at 140 ° C for 30 minutes. The color intensity and its measurement are defined in accordance with DIN EN ISO 787-26. The color strength and color of the pigments obtained in the above examples ( The color purity and hue are shown in the table below. The standard for color intensity (100%), chromaticity Δ C (color purity) (Δ(: = 〇), and hue is the pigment from Comparative Example A. Table 4 : color sample color intensity △ C △ H Example 1 111% -1.17 -1.44 Example 2 113% -1.68 -1.05 Example 3 109% -0.9 -1.25 Example 4 112% -1.44 -1.84 Example 5 116% -0.63 -0.91 Example 6 108% -0.25 -0.37 Example 7 120% -1.58 0.12 Example 8 121% -1.6 0.02 Example 9 113% -1.04 -0.55 Example 10 121% -1.01 -0.78 Example 11 119% -0.89 -0.50 Example 12 125% -0.13 0.22 Example 13 108% -1.41 -0.02 Example 14 111% -1.25 -0.19 Comparative Example A 100% 0.0 0.0 -29- 200902641 For the mixture of cI Pigment Red 25 4 and the pigment dispersant of the present invention in the above ratio as a component, the deviation Δ H in each case is generally expected. And △ (: will be greater than 2.0 to 3.0.

Claims (1)

200902641 X. Patent application scope 1. A pigment preparation 'containing a pigment dispersant having a C I · Pigment Red 2 5 4 and a formula (11 ) having an average particle size d5 () of 20 to 100 nm Wherein Q is an organic pigment group derived from CI Pigment Red 264 and CI Pigment Violet 19; s is a number from 1 to 5; η is a number from 〇 to 4; the sum of s and η is from 1 to 5; R1 is from 1 to a divalent branched or unbranched, saturated or unsaturated aliphatic hydrocarbon group of 20 carbon atoms, or a C5-C7 cycloalkylene group, or a divalent aryl group having 1, 2 or 3 aromatic rings, The aromatic ring may be fused or linked by a bond, or a divalent having 1, 2 or 3 rings and containing 1, 2, 3 or 4 heteroatoms selected from 0, N and S or combinations thereof. a heterocyclic group; the aforementioned hydrocarbon, cycloalkyl, aryl and heteroaryl group may be substituted by 1, 2, 3 or 4 substituents selected from the group consisting of OH, CN, F'Cl, Br, N02, CF3, alkoxy, S-CrCe alkyl, -31 - 200902641 NHCONH2, NHC(NH)NH2, NHCO-Ci-Ce, Ci-C6 alkyl, COOR20, CONR20r2i, NR2〇R2i, S03R2() or S02-NR2QR21 ' R20 and R21 are the same or different and are hydrogen, phenyl or Ci-Cs alkyl; R2 is hydrogen, or R1 or R^-CO (TE+; E+, G + is the first to fifth of the periodic table) Metallic cations of the main group or the ! or 2 or 4 to 8 transition group Mm + Equivalent Mm + /m B m,m is the number 1, 2 or 3; or unsubstituted or substituted money ion. 2 · The pigment preparation of claim 1 of the patent range, which is a number from 1 to 3, And η is a number from 0.2 to 1.5. 3 · As in the pigment preparation of claim 1 or 2, the armor R1 is a branched or unbranched CkCm alkyl or phenyl group. The pigment preparation of item 1 or 2, wherein r1 is an ethyl group, a propyl group or a butyl group. 5. The pigment preparation according to claim 1 or 2, wherein R2 is hydrogen, methyl or ethyl. 6. The pigment preparation according to claim 1 or 2, wherein the &amp; _ cation Mm + is Ca 2+ , Sr 2+ , Ba 2+ or Al 3 + 7. The pigment preparation according to claim 1 or 2, wherein the cj pigment The weight ratio of the red 254 to the pigment dispersant of the formula (II) is between (99.9: 0.1) and (80: 20). 8. The pigment preparation according to claim 1 or 2, wherein the cj pigment red 254 The weight ratio of the pigment dispersant to the formula (II) is between (95: -32-200902641 5) and (8 7 : 13). 9 _ A manufacturing as an application Li range, Paragraph 1 of the method of pigment preparation, which is included in the room and before kneading, wet grinding, dry grinding or finishing or processing of "Order C.I. Pigment Red 254 with the pigment dispersant of formula ([pi) blending. 1 〇 A use of a pigment preparation as claimed in claim 1 for coloring a high molecular weight organic material of natural or synthetic origin. 1 1 • For use in claim 10 of the patent application, it is used to color plastics, resins, varnishes, lacquers, electrophotographic toners and developers, and inks (including printing inks). 1 2 _ For purposes of application No. 1 or 〗 of the patent scope, it is used to color metal varnishes, color filters and inkjet inks. -33- 200902641 七明说图单}The simple number table is the map of the generation of the map. The table of the generation is the table of the case: the table of the case is ''the one or two days Nw/ the eighth, if there is a chemical formula in this case, Please reveal the chemical formula that best shows the characteristics of the invention: (II) η -4-