DE102007011066A1 - Pigment preparations based on diketopyrrolopyrroles - Google Patents

Abstract

The invention relates to a pigment preparation characterized by a content of C.I. Pigment Red 254 having an average particle size of 20 to 100 nm and a pigment dispersant of the formula (II), in which Q <SUP> 1 </ SUP> is a radical of an organic pigment from the group C.I. Pigment Red 264 and C.I. Pigment Violet 19 is.

Description

The The present invention relates to novel pigment preparations with C. I. Pigment Red 254 as the base pigment and certain anionic pigment dispersants.

pigment preparations are combinations of base pigments and so-called pigment dispersants, these are pigments substituted with specific effective groups. The pigment dispersants are added to the pigments to give the Dispersion in the application media, especially in paints, inks and inks to facilitate and to the rheological and coloristic Properties of the pigments to improve. This can, for example the color strength, the transparency and the shine in many Applications are increased.

to Production of color filters are particularly finely divided pigments used to reduce the particle scattering, which leads to a reduction the contrast ratio leads to largely rule out.

das durch eine besonders enge Teilchengrößenverteilung gepaart mit hoher Kristallinität und einer speziellen Absorptionscharakteristik gekennzeichnet ist. Ein solches C. I. Pigment Red 254 kann erhalten werden, indem ein Rohpigment zunächst mit einem anorganischen Salz trocken bei mindestens 80°C gerührt und anschließend einem Knetprozess mit anorganischen Salzen in Gegenwart von organischen Lösungsmitteln ausgesetzt wird. WO 01/04215 discloses a finely divided diketopyrrolopyrrole pigment, CI Pigment Red 254 (I),

which is characterized by a particularly narrow particle size distribution coupled with high crystallinity and a special absorption characteristic. Such a CI Pigment Red 254 can be obtained by first dry-stirring a crude pigment with an inorganic salt at at least 80 ° C and then subjecting it to a kneading process with inorganic salts in the presence of organic solvents.

Based commercial products are available on this known process, which is required for applications where high transparency is required is recommended. However, these pigments are not enough always meets all the requirements of technology. In particular, still existed a need for improvement with regard to transparency, dispersibility and rheology.

The EP-A-1 104 789 describes pigment dispersants based on pigments, such as. B. of diketopyrrolopyrroles or quinacridones.

It the object was to prepare pigment preparations with C.I. Pigment Red 254 as base pigment to provide the high Color strength, low viscosity and as possible slight hue deviation from the base pigment C.I. Pigment Red 254 and especially suitable for color filter applications are.

It it was found that pigment preparations based on C.I. Red 254 of specific particle size and the below pigment dispersants solve this problem, although due to the coloristics of the individual compounds a much larger Color deviation could have been expected.

worin
Q ein Rest eines organischen Pigments aus der Gruppe C. I. Pigment Red 264 und C. I. Pigment Violet 19 ist;
s eine Zahl von 1 bis 5 darstellt;
n eine Zahl von 0 bis 4 darstellt; wobei die Summe von s und n 1 bis 5 beträgt;
R¹ einen bivalenten verzweigten oder unverzweigten, gesättigten oder ungesättigten, aliphatischen Kohlenwasserstoffrest mit 1 bis 20 C-Atomen, oder einen C₅-C₇-Cycloalkylenrest, oder einen bivalenten aromatischen Rest mit 1, 2 oder 3, vorzugsweise 1 oder 2 aromatischen Ringen, wobei die Ringe kondensiert vorliegen oder durch eine Bindung verknüpft sein können, wie beispielsweise ein Phenyl-, Biphenyl- oder Naphthyl-Rest, oder einen bivalenten heterocyclischen Rest mit 1, 2 oder 3 Ringen, der 1, 2, 3 oder 4 Heteroatome aus der Gruppe O, N und S enthält, oder eine Kombination davon bedeutet;
wobei die vorstehend genannten Kohlenwasserstoff-, Cycloalkyl-, Aromaten- und Heteroaromaten-Reste durch 1, 2, 3 oder 4 Substituenten aus der Gruppe OH, CN, F, Cl, Br, NO₂, CF₃, C₁-C₆-Alkoxy, S-C₁-C₆-Alkyl, NHCONH₂, NHC(NH)NH₂, NHCO-C₁-C₆-Alkyl, C₁-C₆-Alkyl, COOR²⁰, CONR²⁰R²¹, NR²⁰R²¹, SO₃R²⁰, COO^–E⁺, SO₃ ^–E⁺ oder SO₂-NR²⁰R²¹ substituiert sein können, wobei R²⁰ und R²¹ gleich oder verschieden sind und Wasserstoff, Phenyl oder C₁-C₆-Alkyl bedeuten;
R² Wasserstoff, R¹ oder R¹-000^–E⁺ bedeutet;
E⁺ und G⁺ das Äquivalent M^{m +}/m eines Metallkations M^m+ aus der 1. bis 5.The invention relates to pigment preparations characterized by a content of CI Pigment Red 254 having a mean particle size d _{50 of} from 20 to 100 nm, and a pigment dispersant of the formula (II)

wherein
Q is a residue of an organic pigment from the group CI Pigment Red 264 and CI Pigment Violet 19;
s represents a number from 1 to 5;
n represents a number from 0 to 4; wherein the sum of s and n is 1 to 5;
R ^{1 is} a bivalent branched or unbranched, saturated or unsaturated, aliphatic hydrocarbon radical having 1 to 20 C atoms, or a C ₅ -C ₇ cycloalkylene radical, or a bivalent aromatic radical having 1, 2 or 3, preferably 1 or 2 aromatic rings wherein the rings may be condensed or linked by a bond, such as a phenyl, biphenyl or naphthyl radical, or a bivalent heterocyclic radical having 1, 2 or 3 rings of 1, 2, 3 or 4 heteroatoms the group contains O, N and S, or a combination thereof;
where the abovementioned hydrocarbon, cycloalkyl, aromatic and heteroaromatic radicals are replaced by 1, 2, 3 or 4 substituents from the group OH, CN, F, Cl, Br, NO ₂ , CF ₃ , C ₁ -C ₆ - Alkoxy, SC ₁ -C ₆ -alkyl, NHCONH ₂ , NHC (NH) NH ₂ , NHCO-C ₁ -C ₆ -alkyl, C ₁ -C ₆ -alkyl, COOR ²⁰ , CONR ²⁰ R ²¹ , NR ²⁰ R ²¹ , SO ₃ R ²⁰ , COO ^- E ⁺ , SO ₃ ^- E ⁺ or SO ₂ --NR ²⁰ R ²¹ , wherein R ²⁰ and R ^{21 are the} same or different and are hydrogen, phenyl or C ₁ -C ₆ alkyl mean;
R ^{2 is} hydrogen, R ¹ or R ¹ -000 ^- E ⁺ ;
E ⁺ and G ⁺ the equivalent M ^{m +} / m of a metal cation M ^{m +} from the 1st to the 5th

Main group or from the 1st or 2nd or the 4th to 8th subgroup of the Periodic Table of the Chemical Elements, where m is one of the numbers 1, 2 or 3, such as Li ^{1 +} , Na ^{1 +} , K ^{1 +} , mg ^2+, Ca ^2+, Sr ^2+, Ba ^2+, Mn ^{2 +,} Cu ^{2 +,} Ni ^{+ 2,} Co ^{+ 2,} Zn ^{+ 2,} Fe ^{+ 2,} Al ^{+ 3,} Cr or Fe ^{+ 3;} or an unsubstituted or substituted ammonium ion.

• (i) N⁺R⁹R¹⁰R¹¹R¹² wobei die Substituenten R⁹, R¹⁰, R¹¹ und R¹² unabhängig voneinander jeweils ein Wasserstoffatom, C₁-C₃₀-Alkyl, C₂-C₃₀-Alkenyl, C₅-C₃₀-Cycloalkyl, Phenyl, (C₁-C₈)-Alkyl-phenyl, (C₁-C₄)-Alkylen-phenyl, beispielsweise Benzyl, oder eine (Poly)alkylenoxy-gruppe der Formel -[CH(R⁸⁰)-CH(R⁸⁰)-O]_k-H sind, in der k eine Zahl von 1 bis 30 ist und die beiden Reste R⁸⁰ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder, sofern k > 1 ist, eine Kombination davon bedeuten; und worin als R⁹, R¹⁰, R¹¹ und/oder R¹² ausgewiesenes Alkyl, Alkenyl, Cycloalkyl, Phenyl oder Alkylphenyl durch Amino, Hydroxy, und/oder Carboxy substituiert sein können; oder wobei die Substituenten R⁹ und R¹⁰ zusammen mit dem quartären N-Atom ein fünf- bis siebengliedriges gesättigtes Ringsystem, das ggf. noch weitere Heteroatome aus der Gruppe O, S und N enthält, bilden können, beispielsweise vom Pyrrolidon-, Imidazolidin-, Hexamethylenimin-, Piperidin-, Piperazin- oder Morpholin-Typ; oder wobei die Substituenten R⁹, R¹⁰ und R¹¹ zusammen mit dem quartären N-Atom ein fünf- bis siebengliedriges aromatisches Ringsystem, das ggf. noch weitere Heteroatome aus der Gruppe O, S und N enthält und an dem ggf. zusätzliche Ringe ankondensiert sind, bilden können, beispielsweise vom Pyrrol-, Imidazol-, Pyridin-, Picolin-, Pyrazin-, Chinolin- oder Isochinolin-Typ; oder
• (ii) ein Ammoniumion der Formel (Ia) bedeutet,
  
  worin R¹⁵, R¹⁶, R¹⁷ und R¹⁸ unabhängig voneinander Wasserstoff oder eine (Poly)alkylenoxygruppe der Formel –[CH(R⁸⁰)-CH(R⁸⁰)O]_k-H bedeuten, in der k eine Zahl von 1 bis 30 ist und die beiden Reste R⁸⁰ unabhängig voneinander Wasserstoff, C₁-C₄-Alkyl oder, sofern k > 1 ist, eine Kombination davon bedeuten; q eine Zahl von 1 bis 10, vorzugsweise 1, 2, 3, 4 oder 5 ist; p eine Zahl von 1 bis 5, wobei p ≤ q + 1 ist; T einen verzweigten oder unverzweigten C₂-C₆-Alkylenrest bedeutet; oder worin T, wenn q > 1 ist, auch eine Kombination von verzweigten oder unverzweigten C₂-C₅-Alkylenresten sein kann.

In the event that E ⁺ or G ^{+ represent} an ammonium ion, are eligible for this:

• (i) N ⁺ R ⁹ R ¹⁰ R ¹¹ R ¹² where the substituents R ⁹ , R ¹⁰ , R ¹¹ and R ¹² independently of one another each represent a hydrogen atom, C ₁ -C ₃₀ -alkyl, C ₂ -C ₃₀ -alkenyl, C C ₅ -C ₃₀ -cycloalkyl, phenyl, (C ₁ -C ₈ ) -alkyl-phenyl, (C ₁ -C ₄ ) -alkylene-phenyl, for example benzyl, or a (poly) -alkyleneoxy group of the formula - [CH ( R ⁸⁰ ) -CH (R ⁸⁰ ) -O] _k -H, in which k is a number from 1 to 30 and the two radicals R ⁸⁰ independently of one another are hydrogen, C ₁ -C ₄ -alkyl or, if k> 1 is to mean a combination of it; and wherein R ⁹ , R ¹⁰ , R ¹¹ and / or R ¹² may be substituted alkyl, alkenyl, cycloalkyl, phenyl or alkylphenyl by amino, hydroxy, and / or carboxy; or where the substituents R ⁹ and R ¹⁰ together with the quaternary nitrogen atom can form a five- to seven-membered saturated ring system optionally containing further heteroatoms from the group O, S and N, for example from the pyrrolidone, imidazolidine Hexamethyleneimine, piperidine, piperazine or morpholine type; or where the substituents R ⁹ , R ¹⁰ and R ¹¹ together with the quaternary nitrogen atom contain a five- to seven-membered aromatic ring system which optionally contains further heteroatoms from the group O, S and N and to which optionally additional rings are condensed are, for example, of the pyrrole, imidazole, pyridine, picoline, pyrazine, quinoline or isoquinoline type; or
• (ii) an ammonium ion of the formula (Ia)
  
  wherein R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ independently of one another denote hydrogen or a (poly) alkyleneoxy group of the formula - [CH (R ⁸⁰ ) -CH (R ⁸⁰ ) O] _k -H, in which k is a number of 1 is up to 30 and the two radicals R ⁸⁰ independently of one another are hydrogen, C ₁ -C ₄ -alkyl or, if k> 1, a combination thereof; q is a number from 1 to 10, preferably 1, 2, 3, 4 or 5; p is a number from 1 to 5, where p ≦ q + 1; T is a branched or unbranched C ₂ -C ₆ -alkylene radical; or wherein T, when q> 1, may also be a combination of branched or unbranched C ₂ -C ₅ -alkylene radicals.

From Of particular interest are pigment dispersants of the formula (II) with s = 1 to 4, n = 0 to 2 and the sum of s and n from 1 to 4. In particular, pigment dispersants of the formula (II) with s = 1 to 3, n = 0.2 to 1.5 and the sum of s and n from 1 to 3 of Interest.

Of particular interest are furthermore pigment dispersants of the formula (II) in which R ^{1 is} a branched or unbranched C ₁ -C ₁₀ -alkylene group, in particular ethylene, propylene or butylene, or a phenylene radical.

Of particular interest are furthermore pigment dispersants of the formula (II) in which R ^{2 is} hydrogen or C ₁ -C ₆ -alkyl, in particular H, methyl or ethyl.

Of particular interest are pigment dispersants of the formula (II) in which ²⁺ or Al mean E ⁺ and G ^{+ is} the corresponding stoichiometric equivalent of Ca ^2+, Sr ^2+, Ba ^3+.

The pigment dispersants of the formula (II) are compounds known per se and can be prepared by known processes, for. B. after EP-B1-1 362 081 ,

In the pigment preparations of the invention the weight ratio of C.I. Pigment Red 254 to pigment dispersant of the formula (II) preferably between (99.9 to 0.1) and (80 to 20), more preferably between (99 to 1) and (83 to 17), in particular between (97 to 3) and (85 to 15), and most preferably between (95 to 5) and (87 to 13).

For a mixture of components C.I. Pigment Red 254 and the invention Pigment dispersant in the claimed ratio would be a deviation of ΔH and ΔC in each case larger to expect 3.0. Chroms (C) is the parameter that determines the chroma describes the color at a given brightness, ΔC describes the difference in the chroma of two colors. Analogously describes ΔH the difference in hue for two colors to compare.

Surprisingly showed, however, that a staining according to DIN EN ISO 787-26 with 1/3 standard color depth in alkyd / melamine resin paint system with one Pigment preparation according to the invention in comparison to a staining of the corresponding pure C.I.P. Red 254 and same particle size a ΔH (according to CIELAB) of preferably not more than 2.0, in particular not more than 1.5, and more preferably not more than 1.0 having. Preferably, the ΔC (after CIELAB) is not larger than 2.0, in particular not greater than 1.5 and more preferably not greater than 1.0.

The pigment preparations according to the invention are preferably highly crystalline, characterized by a half-width HWB of the main peak of 0.2 to 0.7 ° 2Theta, in particular from 0.3 to 0.5 ° 2Theta, in the X-ray powder diffractogram with CuK _alpha radiation.

The pigment preparations according to the invention contain the base pigment having an average particle size d ₅₀ of 20 to 100 nm, preferably 30 to 80 nm. The particle size distribution of CI Pigment Red 254 is preferably approximated to a Gaussian distribution in which the standard deviation sigma is preferably less than 40 nm, more preferably less than 30 nm. As a rule, the standard rejects are between 5 and 40 nm, preferably between 10 and 30 nm.

The Pigment preparations of the invention have surprisingly a very low viscosity, preferably a viscosity from 3 to 50 mPas, measured at 20 ° C with a cone and plate viscometer, z. B. RS75 Fa. Haake.

The Pigment preparations according to the invention can in addition to the Diketopyrrolopyrrolpigment and the pigment dispersant contain other customary auxiliaries or additives, such as surfactants, dispersants, fillers, Adjusting agents, resins, waxes, defoamers, anti-dust agents, Extenders, antistatic agents, preservatives, drying retardants, Wetting agents, antioxidants, UV absorbers and light stabilizers, preferably in an amount of 0.1 to 10 wt .-%, in particular 0.5 to 5 wt .-%, based on the total weight of the pigment preparation.

When Surfactants are anionic or anionic, cationic or cationic and nonionic or amphoteric substances or mixtures thereof Means into consideration.

When anionic substances are, for example, fatty acid taurides, Fatty acid methyltaurides, fatty acid isethionates, Alkylphenylsulfonates, for example dodecylbenzenesulfonic acid, Alkylnaphthalenesulfonates, alkylphenol polyglycol ether sulfates, fatty alcohol polyglycol ether sulfates, Fatty acid amide polyglycol ether sulfates, alkyl sulfosuccinamates, Alkenyl succinic acid half esters, fatty alcohol polyglycol ether sulfosuccinates, Alkanesulfonates, fatty acid glutamates, alkylsulfosuccinates, Fatty Sarcosides; Fatty acids, for example Palmitic, stearic and oleic acid; the salts of these anionic substances and soaps, for example alkali salts of fatty acids, Naphthenic acids and resin acids, for example Abietic acid, alkali-soluble resins, for example rosin-modified maleate resins and condensation products based on cyanuric chloride, taurine, N, N'-diethylaminopropylamine and p-phenylenediamine into consideration. Preferred are rosin soaps, d. H. Alkali salts of resin acids.

When Cationic substances come, for example, quaternary Ammonium salts, Fettaminoxalkylate, polyoxyalkyleneamines, alkoxylated Polyamines, fatty amine polyglycol ethers, primary, secondary or tertiary amines, for example alkyl, cycloalkyl or cyclized alkylamines, in particular fatty amines, of fatty amines or Fatty alcohols derived di- and polyamines and their oxalkylates, derived from fatty acids imidazolines, polyaminoamido or polyamino compounds or resins having an amine index between 100 and 800 mg KOH per g of the polyaminoamido or polyamino compound, and salts of these cationic substances, such as Acetates or chlorides, into consideration.

When Nonionic and amphoteric substances are, for example, fatty amine carboxyglycinates, amine oxides, Fatty alcohol polyglycol ethers, fatty acid polyglycol esters, betaines, such as fatty acid amide N-propyl betaines, phosphoric acid esters of aliphatic and aromatic alcohols, fatty alcohols or Fatty alcohol polyglycol ethers, fatty acid amide ethoxylates, fatty alcohol alkylene oxide adducts and alkylphenol polyglycol ethers.

By nonpigmentary dispersants is meant substances which are not structurally derived from organic pigments. They are added as dispersants either already in the production of pigments, but often also during the incorporation of the pigments into the application media to be dyed, for example in the production of color filters by dispersing the pigments in the corresponding binders. They may be polymeric substances, for example polyolefins, polyesters, polyethers, polyamides, polyimines, polyacrylates, polyisocyanates, block copolymers thereof, copolymers of the corresponding monomers or polymers of one class modified with a few monomers of a different class. These polymeric substances carry polar anchor groups such as hydroxy, amino, imino and ammonium groups, carboxylic acid and carboxylate groups, sulfonic acid and sulfonate groups or phosphonic acid and phosphonate groups, and may also be modified with aromatic, non-pigmentary substances. Nonpigmentary dispersants may also be chemically functional group modified aromatic non-organic pigment derived substances. Nonpigmentary dispersants are known in the art and some are available commercially (eg, Solsperse ^®, Avecia;. Disperbyk ^®, Byk-Chemie, Efka ^®, Efka). In the following, a few types are to be mentioned, but in principle any other substances described can be used, for example condensation products of isocyanates and alcohols, diols or polyols, aminoalcohols or diamines or polyamines, polymers of hydroxycarboxylic acids, copolymers of olefin monomers or vinyl monomers and ethylenically unsaturated carboxylic acids and esters, urethane-containing polymers of ethylenically unsaturated monomers, urethane-modified polyesters, condensation products based on cyanurhalo benzene, nitroxyl compound-containing polymers, polyesteramides, modified polyamides, modified acrylic polymers, combicant-type dispersants of polyesters and acrylic polymers, phosphoric acid esters, triazine-derived polymers, modified polyethers, or dispersants derived from aromatic nonpigmentary substances. These basic structures are often further modified, for example by chemical reaction with other functional groups bearing substances or by salt formation.

The Pigment preparation according to the invention may be used as preferred aqueous press cake or wet granules are used, however, they are usually solid systems of powdered Nature.

object The invention also provides a process for the preparation of a novel process according to the invention Pigment preparation, characterized in that C.I. Pigment Red 254 before or during kneading, wet grinding, dry grinding or finish treatment with the pigment dispersant of the formula (II) added.

For example, the dry components may be mixed in granule or powder form before or after grinding; one component may be added to the other component in wet or dry form, for example by mixing the components in the form of the wet presscake.
The mixing can be carried out, for example, by milling in dry form, in moist form, for example by kneading, or in suspension, or by a combination of these processes. The grinding can be carried out with the addition of water, solvents, acids or grinding aids such as salt.

The Mixing can also be done by adding the pigment dispersant during of the manufacturing process of C.I. Pigment Red 254.

The Addition of the pigment dispersant to C.I. Pigment Red 254 takes place but preferably after the chemical formation of the C.I. pigment Red 254 and before or during the formation of the fine particles.

Especially The addition of the pigment dispersant to the diketopyrrolopyrrole pigment preferably takes place during dry or wet grinding. The thereby formed finely crystalline Pigment preparation may be aftertreatment, in general as Finish, be subjected, for example in water and / or Solvents and usually at elevated temperature, for example, up to 200 ° C, and possibly elevated pressure. The pigment dispersant can also be used after dry or wet grinding, but added before or during the finish. Of course the pigment dispersant can also be divided into partial portions Times are added.

at the drying of a wet pigment preparation can the known drying units are used, such as drying cabinets, Paddle wheel dryer, tumble dryer, contact dryer and in particular Spinflash and spray dryer.

The Draw pigment preparations according to the invention distinguished by their outstanding coloristic and rheological Properties, especially high flocculation stability, light Dispersibility, good rheology, high color strength, transparency and Saturation (Chroms). They are lightweight in many application media and dispersible to high levels of fineness. Such pigment dispersions show excellent rheological properties even at high Pigmentation of lacquer or printing ink concentrates. Also other properties, such as gloss, overcoating fastness, solvent fastness, Alkali and acid fastness, light and weather fastness and high purity of hue, are very good. Furthermore can be mixed with the pigment preparations according to the invention Achieve shades in the red area when using in Color filters are in demand. Here they provide high contrast and also satisfy the other, when used in color filters asked Requirements, such as high temperature stability or steep and narrow absorption bands. You can with high purity and low levels of ions are produced.

The Allow pigment preparations of the invention in principle for pigmenting all high molecular weight organic Use materials of natural or synthetic origin, For example, of plastics, resins, paints, especially metallic paints, Paints, electrophotographic toners and developers, Electret materials, color filters and inks, inks.

High molecular weight organic materials which can be pigmented with the pigment preparations 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, such as for example, fatty acids, fatty oils, resins and their 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 novolacs or resols, urea resins, polyvinyls, such as polyvinyl alcohols, polyvinyl acetals, polyvinyl acetates or polyvinyl ethers, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene or polypropylene, poly (meth) acrylates and copolymers thereof, such as polyacrylic acid esters or polyacrylonitriles, polyamides, polyesters, polyurethanes, coumarone-indene and hydrocarbon resins, epoxy resins , unsaturated synthetic 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.

there it does not matter if the mentioned high molecular weight organic compounds as plastic masses, melts or in Form of spinning solutions, dispersions, paints, coatings or printing inks. Depending on the purpose it proves be advantageous, the pigment preparations of the invention as a blend or in the form of preparations or dispersions to use.

It is also possible, the pigment preparation only during incorporation into the high molecular weight organic medium.

object The present invention is therefore also a high molecular weight organic A material containing a dyeing effective amount of Pigment preparation of the invention.

Based on the high molecular weight organic material to be pigmented the pigment preparation of the invention usually in an amount of 0.01 to 30% by weight, preferably 0.1 to 20% by weight. For color filter applications can also be higher Colorant concentrations are used.

The Pigment preparations according to the invention are also suitable as colorants in electrophotographic toners and developers, such as one- or two-component powder toners (also or two-component developer), magnetic toner, liquid toner, Polymerization toner and special toner.

typical Toner binders are polymerization, polyaddition and polycondensation resins, such as styrene, styrene acrylate, styrene butadiene, acrylate, polyester, Phenolic epoxy resins, polysulfones, polyurethanes, alone or in combination, as well as polyethylene and polypropylene, which contain other ingredients, such as charge control agents, waxes or flow aids, may contain or in retrospect with these additions be modified.

Of others are the pigment preparations according to the invention suitable as a colorant in powders and powder coatings, in particular in triboelectrically or electrokinetically sprayable Powder coatings used for surface coating of objects from, for example, metal, wood, plastic, glass, ceramics, concrete, Textile material, paper or rubber are used.

Furthermore are the pigment preparations of the invention as a colorant in ink-jet inks on aqueous and non-aqueous Basis and in inks which work according to the hot-melt method, suitable.

Ink-jet inks generally contain a total of 0.5 to 15 wt .-%, preferably 1.5 to 8 wt .-%, (calculated dry) of the invention Pigment preparation. Microemulsion inks are based on organic Solvents, water and possibly an additional hydrotropic substance (interface mediator). Microemulsion inks generally contain 0.5 to 15% by weight, preferably 1.5 to 8% by weight of the pigment preparation according to the invention, 5 to 99% by weight of water and 0.5 to 94.5% by weight of organic solvent and / or hydrotropic compound.

"Solvent based ink-jet inks preferably contain 0.5 to 15 wt .-% of Pigment preparation according to the invention, 85 to 99.5 Wt .-% organic solvent and / or hydrotrope compounds.

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, with the preferred melting range between about 60 ° C and about 140 ° C. Hot-melt ink-jet inks exist for. B. substantially from 20 to 90 wt .-% wax and 1 to 10 wt .-% of the pigment preparation of the invention. Furthermore, 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 .-% plasticizer, 0 to 10 wt % Stickiness additive, 0 to 10% by weight trans Parent stabilizer (prevents, for example, crystallization of the waxes) and 0 to 2 wt .-% antioxidant contained.

Especially are the pigment preparations of the invention as a colorant for color filters, both for the additive as well as for subtractive color generation, such as for example in electro-optical systems such as television screens, LCD (liquid crystal displays), charge coupled devices, plasma displays or electroluminescent displays, which in turn are active (twisted nematic) or passive (supertwisted nematic) ferroelectric displays or light-emitting diodes, as well as colorants for electronic inks ("e-inks") or "electronic paper" ("e-paper").

at the production of color filters, both reflective and transparent Color filters, become pigments in the form of a paste or as pigmented Photoresists in suitable binders (acrylates, acrylic esters, polyimides, Polyvinyl alcohols, epoxies, polyesters, melamines, gelatin, caseins) to the respective LCD components (eg TFT-LCD = Thin Film Transistor Liquid Crystal Displays or z. B. ((S) TN-LCD = (Super) Twisted Nematic LCD) applied. In addition to a high thermal stability is for a stable paste or a pigmented photoresist also a high pigment purity requirement. In addition, you can the pigmented color filters also by ink jet printing process or other suitable printing methods.

The Red shades of the pigment preparations according to the invention are especially suitable for the Color Filter color set Red-Green-Blue (R, G, B). These three colors are separated Color dots next to each other in front, and are illuminated from behind a full color picture.

typical Colorants for the red color point are pyrrolopyrrole, Quinacridone and azo pigments, such as. C.I. Pigment Red 254, C. Pigment Red 209, C.I. Pigment Red 175 and C.I. Pigment Orange 38, single or mixed. For the green color point typically phthalocyanine colorants are used, such as. C.I. Pigment Green 36 and C.I. Pigment Green 7.

at Need can the respective color dots even more colors be added for nuancing. For the red and green color is preferably blended with yellow, for example with C.I. Pigment Yellow 138, 139, 150, 151, 180 and 213.

In In the following examples, percentages are by weight and parts by weight unless otherwise stated.

Example 1: Pearl Milling of C.I. Pigment Red 254 in the presence of 10% of the pigment dispersant:

der analog Beispiel 1 der EP-B1-1 362 081 hergestellt wurde, wird in einer Drais^® Advantis V3-Mühle gemahlen. Die Mahldauer entspricht fünf bis sechs theoretischen Mahlpassagen. Das Mahlgut wird von den Perlen getrennt, filtriert und der Filterkuchen mit einer 1:1-Mischung aus Wasser und Isobutanol bei pH 2 für 2 h zum Rückfluss erhitzt. Nach der Wasserdampfdestillation wird abfiltriert, mit Wasser salzfrei gewaschen, im Vakuum getrocknet und abschließend pulverisiert. Man erhält eine rote Pigmentzubereitung mit einer mittleren Teilchengröße d₅₀ von 40 nm (TEM).A mixture of 70 parts of PR 254, 1.4 parts of a commercially available naphthalenesulfonic acid-based flow improver, 800 parts of zirconia beads (0.4-0.6 mm), 600 parts of water and 7 parts of a pigment dispersant of the formula (V),

Analogously to Example 1 of EP-B1-1 362 081 was prepared in a Drais Advantis ^® V3 mill is Gemah len. The grinding time corresponds to five to six theoretical grinding passages. The millbase is separated from the beads, filtered and the filter cake is heated to reflux with a 1: 1 mixture of water and isobutanol at pH 2 for 2 h. After the steam distillation is filtered off, washed free of salt with water, dried in vacuo and finally pulverized. This gives a red pigment preparation having an average particle size d ₅₀ of 40 nm (TEM).

Example 2: Bead grinding of C.I. Pigment Red 254 and adding 10% of the pigment dispersant prior to solvent treatment

A mixture of 90 parts of PR 254, 1.8 parts of a commercially available naphthalenesulfonic acid-based flow improver and 800 parts of water is homogeneously pasted and milled with a Drais® Advantis V3 mill in the presence of 800 parts of zirconia beads (0.4-0.6 mm) , The grinding time corresponds to five to six theoretical grinding passages. 7.40 parts of the 10% grinding suspension are mixed with 7.4 parts of a pigment dispersant (V) and isobutanol to form a 1: 1 mixture of isobutanol and water. The suspension is heated at pH 2 for 2 h to reflux, filtered off after separation of the isobutanol by steam distillation, washed free of salt with water, dried in vacuo and finally pulverized. This gives a red pigment preparation having an average particle size d ₅₀ of 48 nm (TEM).

Example 3: Bead grinding of C.I. Pigment Red 254 in the presence of 5% of the pigment dispersant:

The procedure is analogous to Example 1, except that instead of 7 parts, only 3.5 parts of a pigment dispersant of the formula (V) are used. This gives a red pigment preparation having an average particle size d ₅₀ of 53 nm (TEM).

Example 4: Bead grinding of C.I. Pigment Red 254 in the presence of 10% of the pigment dispersant:

eingesetzt wird. Man erhält eine rote Pigmentzubereitung mit einer mittleren Teilchengröße d₅₀ von 39 nm (TEM).The procedure is analogous to Example 1, except that a pigment dispersant of the formula (VI),

is used. This gives a red pigment preparation having an average particle size d ₅₀ of 39 nm (TEM).

Example 5: Bead grinding of C.I. Pigment Red 254 and adding 10% of the pigment dispersant before solvent treatment:

It The procedure is analogous to Example 2 except that a pigment dispersant of the formula (VI) is used.

A red pigment preparation having an average particle size d ₅₀ of 46 nm (TEM) is obtained.

Example 6: Bead grinding of C.I. Pigment Red 254 in the presence of 5% of the pigment dispersant:

The procedure is analogous to Example 4, but instead of 7 parts, only 3.5 parts of a pigment dispersant of the formula (VI) are used. This gives a red pigment preparation having an average particle size d ₅₀ of 41 nm (TEM).

Example 7: Bead grinding of C.I. Pigment Red 254 in the presence of 10% of the pigment dispersant:

eingesetzt wird. Man erhält eine rote Pigmentzubereitung mit einer mittleren Teilchengröße d₅₀ von 37 nm (TEM).The procedure is analogous to Example 1, except that a pigment dispersant of the formula (VII),

is used. This gives a red pigment preparation having an average particle size d ₅₀ of 37 nm (TEM).

Example 8: Bead grinding of C.I. Pigment Red 254 and adding 10% of the pigment dispersant before solvent treatment:

It The procedure is analogous to Example 2 except that a pigment dispersant of formula (VII) is used.

This gives a red pigment preparation having an average particle size d ₅₀ of 47 nm (TEM).

Example 9: Pearl Milling of C.I. Pigment Red 254 in the presence of 5% of the pigment dispersant:

The procedure is analogous to Example 7, except that instead of 7 parts, only 3.5 parts of a pigment dispersant of the formula (VII) are used. This gives a red pigment preparation having an average particle size d ₅₀ of 37 nm (TEM).

Example 10: Pearl Milling of C.I. Pigment Red 254 in the presence of 10% of the pigment dispersant:

eingesetzt wird. Man erhält eine rote Pigmentzubereitung mit einer mittleren Teilchengröße d₅₀ von 51 nm (TEM).The procedure is analogous to Example 1, except that a pigment dispersant of the formula (VIII),

is used. This gives a red pigment preparation having an average particle size d ₅₀ of 51 nm (TEM).

Example 11: Bead grinding of C.I. Pigment Red 254 and adding 10% of the pigment dispersant before solvent treatment:

It The procedure is analogous to Example 2 except that a pigment dispersant of the formula (VIII) is used.

A red pigment preparation having a mean particle size d ₅₀ of 62 nm (TEM) is obtained.

Example 12: Bead grinding of C.I. Pigment Red 254 in the presence of 5% of the pigment dispersant:

The procedure is analogous to Example 10, but instead of 7 parts, only 3.5 parts of a pigment dispersant of the formula (VIII) are used. This gives a red pigment preparation having an average particle size d ₅₀ of 54 nm (TEM).

Example 13: Pearl Milling of C.I. Pigment Red 254 in the presence of 10% of the pigment dispersant:

The procedure is analogous to Example 7, except that instead of 1.4 parts of a commercially available flow improver based on naphthalenesulfonic acid, 5.6 parts of a 25% solution of a sodium salt of a commercially available Styrolacrylatharzes (M> 15000) is used in water. This gives a red pigment preparation having an average particle size d ₅₀ of 43 nm (TEM).

Example 14: Pearl Milling of C.I. Pigment Red 254 in the presence of 5% of the pigment dispersant:

The procedure is analogous to Example 13, but instead of 7 parts, only 3.5 parts of a pigment dispersant of the formula (VIII) are used. This gives a red pigment preparation having an average particle size d ₅₀ of 41 nm (TEM).

Comparative Example A: Bead grinding of C.I. Pigment Red 254 without a pigment dispersant

A mixture of 90 parts of PR 254, 1.8 parts of a commercial flow improver based on naphthalenesulfonic acid and 800 parts of water is a homogeneous paste with a Drais Advantis ^® V3-mill in the presence of 800 parts of zirconium oxide beads (0.4-0.6 mm) milled , The grinding time corresponds to five to six theoretical grinding passages. The millbase is mixed with isobutanol to give a 1: 1 mixture of isobutanol and water. The suspension is heated at pH 2 for 2 h to reflux, filtered off after separation of the isobutanol by steam distillation, washed free of salt with water, dried in vacuo and finally pulverized. This gives a red pigment preparation having an average particle size d ₅₀ of 102 nm (TEM).

Particle size distribution the samples:

For the particle size distribution becomes a series of electron microscopic Recordings used. The primary particles become visual identified. The area of each primary particle is determined by means of a graphic tablet. Out of the plane the diameter of the area of the same circle is determined. The frequency distribution of the calculated equivalent diameter is determined and the frequencies are converted into volume fractions and shown as a particle size distribution.

The default distribution is a measure of the width of the distribution. The smaller the standard deviation, the narrower the particle size distribution. Table 1: Grain size distribution and standard deviation sample d50 [nm] Standard deviation σ [nm] 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 samples:

Under Half width HWB is the width of the reflex in half Height (half of the maximum) of the largest Peaks (at 28 °).

The half-width of the samples is measured using a STOE / θ diffractometer (Cu-K _α , U = 40 kV, 1 = 40 mA) (aperture: primary side / vertical 2 × 8 mm, primary side / horizontal 1.0 mm, secondary side 0 , 5 mm). The sample carrier used is a standard steel carrier. The measuring time is adapted to the desired statistical safety, the angle range 20 in the overview measurement is 5-30 ° and the step size 0.02 ° with a time period of 3 s. In the special area is measured from 23-30 ° with a step size of 0.02 ° and a time period of 6 s.

The X-ray beam is monochromatized by a graphite secondary monochromator and measured with a scintillation counter with continuous sample rotation. For evaluation, a profile fit is performed over the entire angular range of the second measurement 2θ = 23-30 ° (fit function: Lorentz ² (4 reflexes)). Table 2: crystallinity sample Half width [° 2θ] (main peak) 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 a mill base for Color filter applications:

10 g pigment or pigment preparation from the previously described examples are suspended in 73 g of PGMEA (propylene glycol monomethyl ether acetate), with 17 g of a commercial, high molecular weight block copolymer and 250 g of zirconia beads (0.3 mm) and for three Hours in Paintshaker Disperse DAS 200 from Lau GmbH, dispersed.

To determine the viscosity of the mill base, use a cone and plate Haake RS75 viscometer at 20 ° C. Table 3: Viscosity sample Viscosity [mPas] 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 8th Example 13 12 Example 14 17 Comparative Example A 96

The pigment preparations described are using a spin coater (POLOS Wafer Spinner) on glass plates (SCHOTT, laser cut, 10 × 10 cm).

by virtue of the low viscosities give brilliant, highly transparent, red colorations with a small layer thickness (500 to 1300 nm) and very good contrast value (TSUBOSAKAELECTRIC CO., LTD, model CT-1), which is the color of the non-additive Samples differ only slightly.

The Pigment preparations from Examples 1 to 14 are due to their High contrast value well suited for color filter applications.

Application examples for transparent Burn-in coatings:

to Determination of the color strength, the chroma ΔC and the hue ΔH of the pigment mixtures were the obtained Pigments in a transparent alkyd-melamine stoving lacquer system completely dispersed and obtained a Volltonlack.

Subsequently A whitening varnish was prepared by adding 6.0 grams of the alkyd-melamine stain varnish were mixed with 20.0 g of a 30% white paint.

Of the obtained whitening varnish was used together with the to be compared Sample mounted side by side on a white cardboard card and after 30 min air drying for 30 min at 140 ° C. baked. The color intensity and its measurement is defined according to DIN EN ISO 787-26.

The Color strengths, Chroms (color purity) and the color of the Pigments prepared in the above examples are described in U.S.P. given in the following table.

As a standard for the color strength (100%), the chroma ΔC (color purity) (ΔC = 0) and the hue ΔH (ΔH = 0), the pigment from Comparative Example A was used. Table 4: Coloristics sample color strength .DELTA.C AH 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

For a mixture of components C.I. Pigment Red 254 and the invention Pigment dispersant in the proportions described would be a deviation of ΔH and ΔC respectively greater than 2.0 to 3.0.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 01/04215 [0004]
• - EP 1104789 A [0006]
• - EP 1362081 B1 [0016, 0056]

Claims (12)

1) pigment preparation, characterized by a content of CI Pigment Red 254 having an average particle size d ₅₀ of 20 to 100 nm, and a pigment dispersant of the formula (II)

wherein Q is a residue of an organic pigment from the group CI Pigment Red 264 and CI Pigment Violet 19; s represents a number from 1 to 5; n represents a number from 0 to 4; wherein the sum of s and n is 1 to 5; R ^{1 is} a bivalent branched or unbranched, saturated or unsaturated, aliphatic hydrocarbon radical having 1 to 20 C atoms, or a C ₅ -C ₇ cycloalkylene radical, or a bivalent aromatic radical having 1, 2 or 3 aromatic rings, wherein the rings condensed or a bivalent heterocyclic radical having 1, 2 or 3 rings which contains 1, 2, 3 or 4 heteroatoms from the group O, N and S, or a combination thereof; where the abovementioned hydrocarbon, cycloalkyl, aromatic and heteroaromatic radicals are substituted by 1, 2, 3 or 4 substituents from the group OH, CN, F, Cl, Br, NO ₂ , CF ₃ , C ₁ -C ₅ - Alkoxy, SC ₁ -C ₅ alkyl, NHCONH ₂ , NHC (NH) NH ₂ , NHCO-C ₁ -C ₆ alkyl, C ₁ -C ₆ alkyl, COOR ²⁰ , CONR ²⁰ R ²¹ , NR ²⁰ R ²¹ , SO ₃ R ²⁰ or SO ₂ -NR ²⁰ R ²¹ may be substituted, wherein R ²⁰ and R ^{21 are the} same or different and are hydrogen, phenyl or C ₁ -C ₅ alkyl; R ^{2 is} hydrogen, R ¹ or R ^{1 is} -COO ^- E ⁺ ; E ⁺ and G ⁺ denotes the equivalent M ^{m +} / m of a metal cation M ^{m +} from the 1st to 5th main group or from the 1st or 2nd or the 4th to 8th subgroup of the Periodic Table of the Chemical Elements, where m is a the number is 1, 2 or 3; or an unsubstituted or substituted ammonium ion. Pigment preparation according to Claim 1, characterized that s a number from 1 to 3, and n is a number of 0.2 to 1.5. Pigment preparation according to claim 1 or 2, characterized in that R ^{1 is} a branched or unbranched C ₁ -C ₁₀ alkylene group or a phenylene radical. Pigment preparation according to one or more of claims 1 to 3, characterized in that R ^{1 is} ethylene, propylene or butylene. Pigment preparation according to one or more of claims 1 to 4, characterized in that R ^{2 is} hydrogen, methyl or ethyl. Pigment preparation according to one or more of claims 1 to 5, characterized in that the metal cation M ^{m + has} the definition Ca ^1, Sr ^{2 +,} Ba ²⁺ or Al ³⁺ has. Pigment preparation according to one or more of the claims 1 to 6, characterized in that the weight ratio of C.I. Pigment Red 254 to pigment dispersant of the formula (II) between (99.9 to 0.1) and (80 to 20). Pigment preparation according to one or more of the claims 1 to 7, characterized in that the weight ratio of C.I. Pigment Red 254 to pigment dispersant of the formula (II) between (95 to 5) and (87 to 13). Process for the preparation of a pigment preparation according to or more of claims 1 to 8, characterized C.I. Pigment Red 254 before or during kneading, Wet grinding, dry grinding or finish treatment with the pigment dispersant of the formula (II). Use of a pigment preparation according to one or more of claims 1 to 8 for pigmenting high molecular weight organic materials natural or synthetic Origin. Use according to claim 10 for pigmenting plastics, Resins, paints, paints, electrophotographic toners and Developers, inks and inks. Use according to claim 10 or 11 for pigmenting metallic paints, Color filters and inkjet inks.