ES2360554T3 - AZOIC PIGMENT FINALLY DIVIDED AND PROCEDURE FOR PRODUCTION. - Google Patents

Abstract

Monoazoic pigment of the formula (I) in the beta crystalline phase characterized in that at least 90% by weight of the particles have an equivalent Stokes diameter less than or equal to 130 nm.

Description

In the case of the use of pigments for the staining of high molecular weight organic materials, high requirements are established for the technical properties of pigment applications, such as high chromatic forces, easy dispersibility, high chromaticity (chroma) and High purity of color tone and good fastness against light and against atmospheric conditions. It is desirable to have as universal a suitability as possible for the use in staining of different high molecular weight systems, such as synthetic materials as well as printing inks and aqueous varnishes and containing solvents. Both in the case of varnishes and in the case of printing inks, the trend is directed towards high concentrations of pigment in the ground mass, and therefore concentrates are requested for varnishes and printing inks pigmented in a high degree or milling materials (in millbase English) with a low viscosity, however, also the viscosity of the varnish or the finished printing ink must be adapted to the application. In the case of printing inks, high transparency is required, in the varnish systems, irreproachable fastnesses in the face of over-varnishing and fastnesses in the face of solvents, stability against alkalis and acids and, in particular, in the case, are desired. of metallic varnishes, high transparency and bright color tones. In the case of dyeing synthetic materials, high strength against bleeding, high heat resistance and good dispersibility are requested, which is expressed, for example, in high chromatic forces. In addition, an as universal as possible aptitude is desired for use in different systems, for example in aqueous systems and containing solvents.

Other sectors of use of pigments are for example electrophotographic toners and developers, inks such as for example ink for inkjet printing (in English Ink Jet) or electronic inks (e-inks), chromatic filters, or powder varnishes , which in each case have their additional special requirements.

In the case of color filters (in English color filter), a full color image is generated by means of a transmitted light of image points of red, green and blue colors. Along with the “transmissive” (or “non-emissive”) color filters (= transmitted or backlit light) there are also “reflective” color filters, which can then also work with yellow, cyan and magenta color dots. In the case of chromatic filters, a difference is established between LCD chromatic filters (acronym for liquid crystal display = visual presenter of liquid crystal) of AM (acronym for active matrix = active matrix) and PM (acronym for passive matrix = matrix passive), corresponding to the color filters of LCD -TFT (acronym for thin film transistor = thin film transistors).

In addition, chromatic filters can also be used in the case of MEMS (DMD) (= acronym for Micro-Electro-Mechanical Systems (Digital Micro Mirror Device) = micro-electro-mechanical systems (with digital micro mirror device ), in the case of electronic papers, as well as in other appropriate visual presentation technologies.The visual presenters of chromatic filters find application in the most different electro-optical systems, such as eg in graphic screens of monitors of the type of Desk-Top (horizontal desktop) on computer graphic screens, on laptop graphic screens (in English Laptops, portable computers), PDA (acronym for Personal Digital Assistants = personal digital assistants, pocket computers) as well as on phone monitors mobiles, camcorders, GPS (acronym for global positioning systems = global positioning systems) and other types of moni tores as well as in general in liquid crystal and charge coupled devices (in English charge coupled devices), plasma visual presenters or in electroluminescent and other visual displays. The last mentioned ones can be active ferroelectric visual presenters (twisted nematic, in twisted nematic English) or passive (super-twisted nematic, in English supertwisted nematic) or eg light emitting diodes. In addition, chromatic filters are used in flat panel visual displays (= flat graphic displays) that are increasingly replacing the usual cathode ray television screens or that can generally be used as indicator panels in a arbitrary size for stationary and mobile information.

A typical LCD chromatic filter structure can be schematically described as follows: Between two glass plates is a thin layer with liquid crystals. The upper glass plate has, together with a series of other functional components, the corresponding image points on the outer surface, eg red, green, blue (R, G, B). These image points are framed in black for better contrast, and outwardly the image points R, G, B are protected by an appropriate protective layer against environmental influences, such as scratches. The lower glass plate still contains other functional components such as eg ITO (Indium Tin Oxide = indium tin oxide) and TFT (Thin Film Transistors, thin film transistors), which among other things are used for activation of the individual image points.

If an appropriate light is sent through the lower glass plate (eg a linearly polarized light with a certain wavelength), then the liquid crystal can be adjusted by activation and electronic selection to “light” or “dark "(Or any arbitrary intermediate stage) Correspondingly, the image points of the chromatic filters are supplied with light and for the human eye a corresponding colored, mobile or immobile image is then formed, which is constituted on the basis of R, G,

B.

European patent application document EP-A-0 894 831 discloses quinoxaline monoazoacetarilide pigments, among others a pigment of the formula (I)

image 1

In the disclosed production process, in the first stage the monoazoic pigment is produced by azoic coupling and is isolated as a press cake. In a second stage, in a dipolar aprotic solvent a finish (finish) is carried out with solvent. Example 1 discloses as solvent N-methyl pyrrolidone. By an X-ray spectroscopy it can be shown that, in the case of this solvent, the original alpha crystalline phase, present after azoic coupling, is transformed into the beta crystalline phase. Finishing with

The solvent provides a coarse particle monoazoic pigment of the formula (I) in the beta crystalline phase.

EP-A 1,167,461 describes the production of the beta form of Yellow Pigment 213 in a microreactor.

The alpha and beta crystalline phases of the monoazoic pigment of the formula (I) are distinguished by the following characteristic lines in the powder X-ray diagram (Table 1, Cu-K alpha radiation, double angle of refraction,

20 values of 2 Theta in degrees with an error limit of +/- 0.2 degrees, distances of reticular planes d in Å, relative intensity in percent).

Table 1

Alpha

Beta

2 Theta

d Rel.  2 Theta d Rel.

3.3

26.8 39 6.4 13.9 7

8.0

11.1 100 7.5 11.8 7

8.8

10.0 55 9.2 9.6 86

9.9

8.9 2. 3 10.5 8.4 4

11.0

8.0 16 12.8 6.9 16

12.4

7.1 12 15.0 5.9 fifteen

13.3

6.7 eleven 16.0 5.5 7

14.7

6.0 14 16.8 5.3 5

16.1

5.5 31 17.2 5.2 13

16.7

5.3 twenty 17.5 5.1 5

18.7

4.7 13 19.3 4.6 twenty

19.9

4,5 twenty-one 19.6 4,5 14

22.6

3.9 18 21.2 4.2 6

24.4

3.7 31 21.6 4.1 12

26.4

3.4 67 21.8 4.1 13

32.4

2.8 eleven 22.8 3.9 5

37.2

2.4 eleven 23.9 3.7 2

25.3

3.5 4

26.0

3.4 19

26.6

3.4 100

27.0

3.3 14

27.8

3.2 7

28.9

3.1 5

30.1

3.0 4

32.0

2.8 6

32.3

2.8 6

33.0

2.7 3

A monoazoic pigment of the formula (I) of coarse particles in the beta crystalline phase is distinguished by a high hiding power and by a good ability to flow in varnishes. In different applications, however, they are sought

5 properties that cannot be achieved by means of a coarse particle pigment, for example a coarse particle pigment leads, in the ink for inkjet printing, to the clogging of the nozzles and does not lead to the high transparency requested in Inkjet printing. Also, a high hiding power is prohibitive for the use of a pigment in printing inks.

There was a need for a finely divided, transparent and well dispersible monoazoic pigment of formula 10 (I) in the beta crystalline phase and a process for its production

It was found that the monoazo pigment of the formula (I) is surprisingly obtainable in its beta crystalline phase as well as in a finely divided, transparent and well dispersible form, when the alpha crystalline phase is subjected to a kneading in a salt.

The object of the invention is a monoazoic pigment of the formula (I) in the finely divided beta crystalline phase, which

15 is characterized in that at least 90% by weight of the particles have an equivalent Stokes diameter less than or equal to 130 nm, preferably less than or equal to 100 nm.

The finely divided monoazoic pigment of the formula (I), according to the invention, is distinguished by good dispersibility. This is shown by determining the equivalent diameter of Stokes in the dispersion. The good dispersibility and the low diameter of the particles lead to high transparency. Transparency can be described with the contrast ratio C = Ys / Yw, Ys being the reference value of clarity on black and Yw being the reference value of clarity on white, and Y being one of the three color values standardized X / Y / Z, which form the basis for the different color systems. In the case of the monoazoic pigment of the formula (I) in the beta crystalline phase according to the invention, the values of the contrast ratio C = Ys / Yw are located at less than or equal to 0.22, preferably less than or equal than 0.20, particularly minor or

25 equal to 0.18.

The object of the invention is also a process for the production of the monoazoic pigment of the formula (I) in the finely divided beta crystalline phase, characterized in that a monoazoic pigment of the formula (I) in The alpha crystalline phase is kneaded in a salt. The alpha crystalline phase of the monoazoic pigment of the formula (I) can be produced for example by coupling azoic, as described in EP-A-0 894 831.

Kneading in a salt is done by kneading the monoazo pigment of the formula (I) in the alpha crystalline phase with an organic liquid and with a crystalline salt in the form of a kneaded, highly viscous paste.

As a salt, salts of mono-, bi- or trivalent metal ions come into question, such as example ions of alkali or alkaline earth metals, with inorganic acids, for example hydrochloric acid, sulfuric acid or acid phosphoric, or with organic acids having 1 to 6 carbon atoms, for example formic acid and acetic acid. Preferred salts are sodium formate; sodium or calcium acetate, sodium citrate, potassium and sodium tartrate; sodium, potassium, calcium, zinc or aluminum chloride; sodium or aluminum sulfate; calcium carbonate; or mixtures of these salts, and in particular sodium chloride. Salts are used in most cases in a larger amount, for example in a multiple amount of 1 to 10 times, preferably 2 to 8 times, in particular 3 to 6 times, referred to the weight of the monoazoic pigment. Even larger quantities can also be used, but These are uneconomic. A usual commercial salt can be coarse-grained and can be shredded, before use in the case of kneading in a salt, by grinding.

The organic liquid is used in amounts such that the grinding material forms a dough and viscose. The quantities used are based on experience between a multiple quantity of 0.05 a 0.8 times, preferably between 0.1 and 0.4 times, in particular between 0.12 and 0.35 times, based on the weight of the mixture of monoazoic pigment and salt. As organic liquids, those in which the Monoazoic pigment and salt are as insoluble as possible. Examples of such organic liquids are alcohols with 4 to 10 C atoms, such as for example butane, such as n-butanol, iso-butanol, tert.butanol, pentaols such as n-pentanol, 2-methyl-2-butanol, hexanols, such as 2- methyl-2-pentanol, 3-methyl-3pentanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, octanoles, such as 2,4,4-trimethyl-2-pentanol, cyclohexanol; or glycols, such as ethylene glycol, di-, tri- or tetra (ethylene glycol), propylene glycol, di-, tri- or tetra (propylene glycol), sorbitol or glycerol; polyglycols, such as poly (ethylene glycols) or poly (propylene glycols); ethers, such as methyl isobutyl ether, tetrahydrofuran, dimethoxyethane or dioxane; ethers of glycols, such as the monoalkyl ether of ethylene- or propylene glycol or di (ethylene glycol), the alkyl being able to represent methyl, ethyl, propyl and butyl, for example butyl glycols or methoxy butanol; monomethyl ethers of poly (ethylene glycols), in particular those having an average molar mass of 350 to 550 g / mol, and dimethyl ethers of poly (ethylene glycols), in particular those having an average molar mass of 250 to 500 g / mol; ketones, such as methyl isobutyl ketone, methyl ethyl ketone or cyclohexanone; acid amides aliphatics, such as formamide, dimethylformamide, N-methyl acetamide or N, N-dimethyl acetamide; urea derivatives, such as tetramethyl urea; or cyclic amides of carboxylic acids, such as N-methyl-pyrrolidone, valero-o caprolactam; esters, such as C1-C6 glycol esters with carboxylic acids; or dialkyl esters of acid phthalic or alkyl esters of benzoic acid. such as C1-C4 alkyl esters with benzoic acid or diesters C1-C12 alkyl with phthalic acid; cyclic esters, such as caprolactone; nitriles, such as acetonitrile, aliphatic or aromatic amines, such as, for example, dimethylaniline or diethylaniline; aliphatic hydrocarbons or halogenated aromatics such as carbon tetrachloride, tri- or tetrachloroethylene; or benzene substituted with alkoxy, nitro, cyano or halogen, for example anisole, nitrobenzene, dichlorobenzenes, trichlorobenzenes or benzonitrile; aromatic heterocycles, such as pyridine, morpholine, picoline or quinoline; 1,3-dimethyl-2-imidazolidinone; sulfones and sulfoxides, such as dimethylsulfoxide and sulfolane; as well as mixtures of these organic liquids. They prefer glycols and ethers of glycols, such as ethylene glycol, di (ethylene glycol) or butyl glycol, dimethylformamide, N-methyl pyrrolidone, dimethylsulfoxide, in particular di (ethylene glycol), N-methyl-pyrrolidone and dimethylsulfoxide. However it is possible, but generally unwanted, use a small amount of water, which should not amount to more than 25% in Total liquid weight including water, which may be contained in the monoazoic pigment used.

In the case of kneading in a salt certain acids, in particular some acids, can also be used which have a pK value less than 4.8. Preferably, phosphoric acid, acids can be used. carboxylic acids, such as acetic acid, dodecyl benzene sulfonic acid and in particular sulfuric acid. The duration of the kneading is oriented to the requirements to be achieved and at the time of change of the crystalline phase, this can be from 30 minutes to 48 hours or longer; in most cases It is located in the range of 1 to 24, in particular 2 to 8 hours.

As usual kneaders, single-arm or multi-arm kneaders come into consideration, continuous and discontinuous, preferably two-arm discontinuous kneading machines, which exert forces of Shear as high as possible on the dough. Usual forms of pallets are pallets double depression (also called palettes in sigma or Z) or chewing palettes. The temperature when kneading is located above the melting point and below the point of boiling of the organic liquid.

Preferably, it is kneaded at a temperature of -20 to 150 ° C, in particular 50 to 120 ° C, with a multiple amount of 4 to 6 times, based on the weight of the monoazoic pigment, of sodium chloride as salt and with a multiple amount of 1 to 2 times, based on the weight of the monoazoic pigment, of di (ethylene glycol) as an organic liquid.

During kneading, if necessary, by subsequently adding an organic liquid and / or a salt, the viscous consistency of the kneaded dough can be adjusted or maintained constantly. The consistency of the kneaded dough can be modified during kneading for example by evaporation of the organic liquid or by grinding the monoazo pigment to give smaller grain sizes.

Prior to kneading, a dry pre-milling of a monoazoic pigment with a salt can be carried out in principle, as described for example in EP-A-1 411 091.

The salt used in the case of kneading in a salt and the organic liquid are preferably removed by an aqueous extraction at an acidic pH value. In this context, acids are used in most cases, which accelerate the dissolution of the salt used, such as, for example, hydrochloric, sulfuric or acetic acid. In most cases, a pH of less than 3 is adjusted, preferably 1 to 2, or extracted by stirring in a 1 to 10% by weight acid. Organic solvents can also be added for extraction. The extraction can be carried out at an arbitrary temperature, as long as the medium remains liquid, possibly also located above the boiling point of the mixture. Since it is preferably worked in an aqueous medium, temperatures between 0 and 100 ° C, in particular between 60 ° C and the boiling temperature, are chosen.

The monoazoic pigment of the formula (I) in the beta crystalline phase, produced according to the process according to the invention, can be isolated with the usual methods, for example by filtration, decantation or centrifugation. Preferably filtered. Solvents can also be removed by washing. The monoazoic pigment according to the invention is preferably used in a dried solid form, in a powdery constitution capable of running or as a granulate, but also as a press cake for example aqueous.

In the monoazoic pigment of the formula (I) finely divided according to the invention, traces or small amounts of the monoazoic pigment of the formula (I) may still be contained in the alpha crystalline phase, but these are proportions below 10% by weight, preferably below 5% by weight. Usually, the transformation of the crystalline phases is carried out by the method according to the invention in such a complete way that, in the X-ray diffraction diagram, the alpha crystalline phase is no longer visible.

In the case of kneading in a salt, when extracting, press cake or also after drying, other auxiliary agents can be added, such as for example surfactants, non-pigmentary and pigmentary dispersing agents, fillers , adjusting agents, resins, waxes, antifoaming agents, antistatic agents, anti-dust release agents, spreading agents, coloring agents for shading, preservatives, drying delay agents, additives for rheology regulation, wetting agents, antioxidant agents, UV absorbing agents, light stabilizing agents, biocides, or a combination of them.

Anionic or anionically active, cationic or cationically active and non-ionic or amphoteric substances, or mixtures of these agents come into consideration as surfactants.

The concept of non-pigment dispersing agents means substances that are not structurally derived from organic pigments. They are added as dispersive agents or already during the production of pigments, often, however, when the pigments are incorporated into the application media to be dyed, for example when the production of varnishes or inks of dispersion printing of the pigments in the corresponding binding agents.

The concept of pigment dispersing agents means pigment dispersing agents known per se, which are derived from an organic pigment as a base body and which are produced by a chemical modification of this base body, for example, pigment dispersing agents containing saccharin. , pigment dispersing agents containing piperidyl, pigment dispersing agents derived from perylene or naphthalene, pigment dispersing agents with functional groups, which are attached to the pigment base body through a methylene group, modified pigment base bodies chemically with polymers, pigmentary dispersing agents containing sulfonic acid groups, sulfonamides or sulphonic acid esters, pigmentary dispersing agents containing ether or thioether groups, or pigmentary dispersing agents containing carboxylic acid groups, carboxylic acid esters or carboxamides Preferably those pigment dispersing agents that are structurally derived from organic pigments with their own yellow color are used as the base body.

In the process according to the invention one or more pigment dispersing agents can be used in a total proportion of 0.1 to 25% by weight, preferably 0.5 to 20% by weight, in particular 1.0 to 17 , 5% by weight, based on the weight of the monoazoic pigment. Anionic groups of the non-pigmentary and pigment dispersing agents, of the surfactants or of the resins, which are used as auxiliary agents, can also be presented with ions of valence 1, 2 or 3 in the form of salts, in particular bound, by example by Ca, Mg, Ba, Sr, Mn or Al ions or by quaternary ammonium ions. The concept of loading materials and extenders respectively means a large number of substances in accordance with DIN 55943 and DIN EN 971-1, for example the different types of talc, kaolin, mica, dolomite, lime, barium sulfate or titanium dioxide.

It was surprising and not foreseeable that the change of the crystalline modification from alpha to beta can be established not only by the known solvent finish, but also by a kneading in a salt. It was also surprising that a new monoazoic pigment of the formula (I) results in the finely divided beta crystalline modification, with properties not known until now. The monoazoic pigment according to the invention is distinguished by outstanding color and rheological properties, in particular high stability against flocculation, easy dispersibility, good rheology, chromatic strength, transparency and high saturation (chroma). He is dispersible in many means of application with ease and even reach high finesse. Such pigment dispersions show outstanding rheological properties even in the case of high pigmentation of the concentrates for varnishes or for printing inks. Other properties are also very good, such as, for example, gloss, fastness against overcoating, solidity against solvents, solidity against alkalis and acids, fastnesses against light and atmospheric conditions and The purity of the color tone. The monoazoic pigment according to the invention can be used excellently in chromatic filters. In this context, he seeks a high contrast and also satisfies the other requirements established in the case of use in chromatic filters, such as high thermal stability or steep and narrow absorption bands. It is also suitable for example for applications in inkjet printing by its high color strength, by good storage stability in the case of low ink viscosity for inkjet printing, which does not show any obstruction of the nozzles and shows high transparency.

The monoazoic pigment according to the invention can be used for the pigmentation of high molecular weight organic materials of natural or synthetic origin, for example of synthetic materials, resins, varnishes, powder varnishes, coloring agents for paints, toners and electrophotographic developers, materials for electrets, color filters, as well as inks, printing inks and seeds.

High molecular weight organic materials, which can be pigmented with the monoazoic pigment according to the invention, are for example certain cellulose compounds, such as for example cellulose ethers and esters such as an ethyl cellulose, a nitrocellulose, acetates of cellulose or cellulose butyrates, natural binding agents, such as for example fatty acids, fatty oils, resins and their transformation products or synthetic resins, such as polycondensates, polyducts, polymers and copolymers, such as for example aminoplasts, in particular resins of formaldehyde with urea and with melamine, alkyd resins, acrylic resins, phenoplasts and phenolic resins, such as novolacs or resoles, urea resins, polyvinyl polymers such as polyvinyl alcohols, polyvinyl acetals, polyvinyl acetates vinyl) or poly (vinyl ethers), polycarbonates, polyolefins, such as a polystyrene, a poly (vinyl chloride), a p olyethylene or a polypropylene, poly (meth) acrylates and their copolymers, such as polyesters of acrylic acid or poly (acrylonitriles), polyamides, polyesters, polyurethanes, coumarone and indene resins and hydrocarbons, epoxy resins, unsaturated synthetic resins (polyesters, acrylates) with the different hardness mechanisms, waxes, aldehyde and ketone resins, vulcanized rubber, natural rubber and its derivatives and latexes, casein, silicones and silicone resins; individually or in mixtures. In this case, it does not perform any task if the aforementioned high molecular weight organic compounds are presented as plastic doughs, melts or in the form of spinning solutions, dispersions, varnishes, paints or printing inks. Depending on the purpose of use, it is advantageous to use the monoazo pigment according to the invention as a prepared mixture (in English blend) or in the form of preparations or dispersions.

The object of the present invention is also a high molecular weight organic material, which contains a coloristically effective amount of the monoazoic pigment of the formula (I) in the beta crystalline phase according to the invention. Referring to the high molecular weight organic material, which is to be pigmented, the monoazo pigment according to the invention is used in most cases in a proportion of 0.01 to 30% by weight, preferably 0.1 at 15% by weight. The monoazoic pigment according to the invention is also suitable as a coloring agent in electrophotographic toners and developers, such as, for example, single component or two component powder toners (also called single component or two component developers), magnetic toners, liquid toners, polymerization toners as well as special toners. Typical binding agents for toners are polymerization, polyaddition and polycondensation resins, such as epoxy resins of styrene, styrene and acrylate, styrene and butadiene, acrylate, polyesters or phenols, polysulfones, polyurethanes, individually

or in combination, as well as a polyethylene and a polypropylene, which may still contain other constituent substances, such as regulators of electric charges, waxes or fluidity aids or which are subsequently modified with these additives.

Moreover, the monoazo pigment according to the invention is suitable as a coloring agent in powders and powder varnishes, in particular in triboelectrically or electrokinetically projectable powder varnishes, which are then used for surface coating of objects made for example of a / a metal, wood, synthetic material, glass, ceramic material, concrete, textile material, paper or rubber.

In addition, the monoazoic pigment according to the invention is suitable as a coloring agent in inks for inkjet printing on an aqueous and non-aqueous base, as well as in those inks that work according to the hot melt process (Hot-Melt in English). ). In inkjet printing inks the monoazoic pigment according to the invention may also be colored with other coloring agents, such as for example inorganic or organic pigments and / or colorants. In this case, it is used in ink sets, which are composed of yellow, magenta, cyan and black inks, which contain certain pigments and / or dyes as coloring agents. For the rest, they can be used in ink sets, which additionally contain one or more of the so-called "spot colors" in colors, for example, orange, green, blue, gold and silver. In this context, a set of printing inks is preferred, whose black preparation preferably contains carbon black as a coloring agent, in particular a gas or furnace carbon black; whose cyan color preparation preferably contains a pigment chosen from the set consisting of the phthalocyanine, indantrone or triarylcarbonium pigments, in particular the blue pigments of the Color Index Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 16, Pigment Blue 56, Pigment Blue 60 or Pigment Blue 61; whose magenta preparation preferably contains a pigment chosen from the group consisting of monoazoic, disazoic, β-naphthol, naphthol AS, linked azoic, metal complexes, benzimidazolone, antantrone, anthraquinone, quinacridone, dioxazine, pigments. perylene, thio-indigo, triarylcarbonium or dicetopyrrolopyrrole, in particular the red or violet pigments of the Color Index Pigment Red 2, Pigment Red 3, Pigment Red 4, Pigment Red 5, Pigment Red 9, Pigment Red 12, Pigment Red 14, Pigment Red 38, Pigment Red 48: 2, Pigment Red 48: 3, Pigment Red 48: 4, Pigment Red 53: 1, Pigment Red 57: 1, Pigment Red 112, Pigment Red 122, Pigment Red 144, Pigment Red 146, Pigment Red 147, Pigment Red 149, Pigment Red 168, Pigment Red 169, Pigment Red 170, Pigment Red 175, Pigment Red 176, Pigment Red 177, Pigment Red 179, Pigment Red 181, Pigment Red 184, Pigment Red 185, Pigment Red 187, Pigment Red 188, Pigment Red 207, Pigment Red 208, Pigment Red 209, Pigment Red 210, Pigment Red 214, Pigment Red 242, Pigment Red 247, Pigment Red 253, Pigment Red 254, Pigment Red 255, Pigment Red 256, Pigment Red 257, Pigment Red 262, Pigment Red 263, Pigment Red 264, Pigment Red 266, Pigment Red 269, Pigment Red 270, Pigment Red 272, Pigment Red 274, and Pigment Violet 19, Pigment Violet 23 or Pigment Violet 32; whose yellow preparation preferably contains a pigment chosen from the set consisting of monoazoic, disazoic, benzimidazoline, isoindolinone, isoindoline or perinone pigments, in particular the yellow pigments of the Color Index Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 73, Pigment Yellow 74, Pigment Yellow 81, Pigment Yellow 83, Pigment Yellow 87, Pigment Yellow 97, Pigment Yellow 111, Pigment Yellow 120, Pigment Yellow 126, Pigment Yellow 127, Pigment Yellow 128, Pigment Yellow 139, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 155, Pigment Yellow 173, Pigment Yellow 174, Pigment Yellow 175, Pigment Yellow 176, Pigment Yellow 180, Pigment Yellow 181, Pigment Yellow 191, Pigment Yellow 194, Pigment Yellow 196, Pigment Yellow 213 or Pigment Yellow 219; whose orange preparation preferably contains a pigment chosen from the set consisting of the disazo, pigment, β-naphthol, naphthol AS, benzimidazolone or perinone pigments, in particular the orange pigments of the Color Index Pigment Orange 5, Pigment Orange 13, Pigment Orange 34, Pigment Orange 36, Pigment Orange 38, Pigment Orange 43, Pigment Orange 62, Pigment Orange 68, Pigment Orange 70, Pigment Orange 71, Pigment Orange 72, Pigment Orange 73, Pigment Orange 74 or Pigment Orange 81; whose preparation of green color preferably contains a pigment chosen from the set consisting of the phthalocyanine pigments, in particular the green pigments of the Color Index Pigment Green 7 or Pigment Green 36. Additionally, the ink sets may still contain shading dyes. , preferably chosen from the set formed by CI Acid (acid) Yellow 17 and C.I. Acid Yellow 23; C.I. Direct (direct) Yellow 86, C.I. Direct Yellow 98 and C.I. Direct Yellow 132; C.I. Reactive (reagent) Yellow 37; C.I. Pigment Yellow 17, C.I. Pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 97, C.I. Pigment Yellow 120, C.I. Pigment Yellow 139, C.I. Pigment Yellow 151, C.I. Pigment Yellow 155 and C.I. Pigment Yellow 180; C.I. Direct Red 1, C.I. Direct Red 11, C.I. Direct Red 37, C.I. Direct Red 62, C.I. Direct Red 75, C.I. Direct Red 81, C.I. Direct Red 87, C.I. Direct Red 89, C.I. Direct Red 95 and C.I. Direct Red 227; C.I. Acid Red 1, C.I. Acid Red 8, C.I. Acid Red 80, C.I. Acid Red 81, C.I. Acid Red 82, C.I. Acid Red 87, C.I. Acid Red 94, C.I. Acid Red 115, C.I. Acid Red 131, C.I. Acid Red 144, C.I. Acid Red 152, C.I. Acid Red 154, C.I. Acid Red 186, C.I. Acid Red 245, C.I. Acid Red 249 and C.I. Acid Red 289; C.I. Reactive Red 21, C.I. Reactive Red 22, C.I. Reactive Red 23, C.I. Reactive Red 35, C.I. Reactive Red 63, C.I.

Reactive Red 106, C.I. Reactive Red 107, C.I. Reactive Red 112, C.I. Reactive Red 113, C.I. Reactive Red 114, C.I. Reactive Red 126, C.I. Reactive Red 127, C.I. Reactive Red 128, C.I. Reactive Red 129, C.I. Reactive Red 130, C.I. Reactive Red 131, C.I. Reactive Red 137, C.I. Reactive Red 160, C.I. Reactive Red 161, C.I. Reactive Red 174 and C.I. Reactive Red 180.

Inkjet printing inks generally contain a total of 0.5 to 15% by weight, preferably 1.5 to 8% by weight, (calculated in the dry state) of the monoazoic pigment according to the invention . The 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 monoazoic pigment according to the invention, 5 of 99% by weight of water and 0 , 5 to 94.5% by weight of an organic solvent and / or hydrotrope compounds. Solvent-based inkjet printing ink (solvent based) preferably contains from 0.5 to 15% by weight of the monoazoic pigment according to the invention, from 85 to 99.5% by weight of at least one organic solvent and / or hydrotropic compounds. Hot melt inks (in English hot-melt inks) are based in most cases on waxes, fatty acids, fatty alcohols or sulphonamides, which are solid at room temperature and become liquid when heated, being located the preferred melting range between about 60 ° C and about 140 ° C. Hot melt inkjet printing inks are composed, for example, essentially from 20 to 90% by weight of a wax and from 1 to 10% by weight of the monoazo pigment according to the invention. In addition, from 0 to 20% by weight of an additional polymer (as "dye solvent"), from 0 to 5% by weight of a dispersing aid, from 0 to 20% by weight of a modifying agent can be contained. the viscosity, from 0 to 20% by weight of a plasticizing agent, from 0 to 10% by weight of an additive for conferring tack, from 0 to 10% by weight of a transparency stabilizing agent (which prevents, e.g. a crystallization of the waxes) as well as 0 to 2% by weight of an antioxidant agent.

In addition, the monoazoic pigment according to the invention is also suitable as a coloring agent for chromatic filters, for the generation of both additive and subtractive colors, such as for example in electro-optical systems, such as television screens, LCD (visual displays of liquid crystals), charge-coupled devices, plasma visual presenters or electroluminescent visual presenters, which in turn can be active ferroelectric (twisted nematic) or passive (super-distorted nematic) or light emitting diode visual displays, as well as dye-emitting diodes for electronic inks ("electronic inks" or "e-inks") or for electronic papers = "electronic paper" ("e-paper"). In the case of the production of chromatic filters, namely both reflective and transparent chromatic filters, pigments are applied in the form of a paste or as pigmented protective masks in appropriate binding agents (acrylates, acrylic esters, polyimides, polyvinyl alcohols), epoxides, polyesters, melamines, jellies, caseins), on the respective component parts of LCD (eg TFT-LCD = Thin Film Transistor Liquid Crystal Displays = visual presenters of liquid crystal with thin film transistors), or e.g. . ((S) TN-LCD = (Super) Twisted Nematic-LCD = nematic (super) twisted liquid crystal visual displays). Together with a high thermostability, a precondition for a stable paste or for a pigmented photomask is also a high purity of the pigments. In addition to this, pigmented chromatic filters can also be applied by inkjet printing procedures or other appropriate printing procedures.

Very special requirements are established for the coloring agents used in the case of chromatic filter materials.

As the most important most important technical parameters, which must be met, we can mention:

-a high thermostability: during the production process of a chromatic filter the individual applied layers are heated, so that the monoazo pigment of the formula (I) in the beta crystalline phase must withstand temperatures up to 300 ° C for up to 1 hour;

-a good dispersibility of the color filter system; -steep and narrow absorption bands of the chromatic filter layer in each case applied; -a high contrast; -a good and stable viscosity in the chromatic filter medium: A too high viscosity prevents the

uniform distribution of the liquid on the glass substrate and thereby impairs the image quality; -ecotoxicological safety when processing,

- a non-flocculating behavior - a surface as smooth as possible (= not rough) of the chromatic filters (pigmented) applied -a stability against acids (eg for the chemical attack procedure (in English etching)) -a solidity against solvents.

The object of the invention is also a chromatic filter, which contains the monoazoic pigment according to the invention in a coloristically effective amount.

The yellow hue of the monoazoic pigment according to the invention is well suited for shading, in special color shades of red and green, from the color set of color filters red - green - blue (R, G, B). These three colors are presented as separate color points next to each other, and provide backlit from behind a full color image. Typical coloring agents for the color point red are pyrrolopyrrole, quinacridone and azo pigments such as e.g. P.R. 254, P.R. 209, P.R. 175 and P.O. 38, individually or mixed. Phthalocyanine dyes such as e.g. P.G.36 and P.G.7 are typically used for the green dot. For the blue dot, non-halogenated or halogenated phthalocyanine dyes are typically used only to a low degree, such as e.g. the P.B. 15: 6 If necessary, other colors can be added to the respective color points for shading.

In order to assess the properties of pigments in the varnish sector in based varnish systems in solvents and anhydrous, a resin varnish was selected from the large number of known varnishes alkyd and melamine based on a medium alkyd oil resin and a melamine resin etherified with butanol (= AM).

The determination of the color properties was carried out in accordance with DIN 55986. The viscosity was determined after dilution of the grinding material to the concentration. final pigment, with the visco-spatula according to Rossmann, type 301 of the Erichsen entity. In the following Examples, the percentage data means so many percent by weight and the parts mean parts by weight, as long as nothing else is indicated.

EXAMPLES

Example 1 187.5 g of the monoazoic pigment of the formula (I) in the alpha crystalline modification, produced in a manner corresponding to Example 1 of EP-A-0 894 831, realizing that, after the synthesis of the cake Press washed until free of salts that has been obtained, dried and suppressed the treatment in N-methylpyrrolidone, kneaded with 1,125 g of micronized sodium chloride (= reduced to a micrometer size) and 330 ml of di (ethylene glycol ) for 8 hours at 85 ° C in a kneader with sigma-shaped paddles. The kneaded dough is stirred in 8 liters of 5% sulfuric acid by weight for 2 hours at 40 ° C, the suspension is filtered with suction, the press cake is washed with water until free of salts and dried at 80 ° C, and the granulate is pulverized. 180 g of the monoazoic pigment of the formula (I) are obtained in the beta crystalline modification. In the powder X-ray diagram, nothing of the alpha crystalline modification can be recognized anymore. 90% by weight of the particles have an equivalent Stokes diameter less than or equal to 93 nm.

Comparative Example 1 When the monoazoic pigment of the formula (I) in the beta crystalline phase is produced in accordance with Example 1 of EP-A-0 894 831, a coarse particle monoazoic pigment results; 90% by weight of the particles have an equivalent Stokes diameter less than or equal to 347 mm.

Example 2 15 g of the monoazoic pigment of the formula (I) in the alpha crystalline modification, produced in a manner corresponding to Example 1 of EP-A-0 894 831, realizing that, after the synthesis of the washed press cake until it is free of salts that has been obtained, it is dried and the treatment in N-methylpyrrolidone is suppressed, they are kneaded with 90 g of micronized sodium chloride in 35 ml of dimethylsulfoxide for 2 hours at 25 ° C in a mixer with paddles in the form of sigma.

The kneaded dough is stirred in 8 liters of 5% sulfuric acid by weight for 2 hours at 40 ° C, the suspension is filtered with suction, the press cake is washed with water until free of salts and dried at 80 ° C, and the granulate is pulverized. 9 g of the monoazoic pigment of the formula (I) are obtained in the beta crystalline modification. In the powder X-ray diagram, nothing of the alpha crystalline modification can be recognized anymore. 90% by weight of the particles have an equivalent Stokes diameter less than or equal to 127 nm.

Description of the measurement method for the determination of Stokes equivalent particle size diameter:

For the determination of the Stokes equivalent particle diameter, the chromatic filter pastes described below are used. Diluted chromatic filter pastes are measured, according to usual methods for the determination of particle size distribution by means of photosedimentometry (compare Herbst and Hunger, Industrial Organic Pigments, VCH 2004, pages 31-33 and 37-41 and ST Fitzpatrick, Polymer News, 1999, Vol 24, No. 2, pages 42-50) in the DC24000 disk centrifuge from CPS Instruments, Inc., Stuart, Florida 34997, USA. Dilution and measurement are carried out with, or respectively, in an organic medium adapted to chromatic filter pastes. The DC24000 is operated with a speed of 20,000 min-1. After having reached this speed, the centrifuged liquid (in English spinfluid) is introduced and loaded into the disc. In the centrifuged liquid a density gradient is generated by the addition of 10-25% (v / v = volume / volume) of bis (3,5,5-trimethyl-hexyl) phthalate in "CB". "CB" is a mixture of cyclohexanone and n-butyl acetate (2: 3 according to weight). 0.1 ml of the chromatic filter pastes diluted to 1: 100 with "CB" and sonorized in an ultrasonic bath are applied on 13.8 ml of the centrifuged liquid. The extinction of a blue light (wavelength 470 nm) is measured, which is based on the dispersion and absorption of particles, which pass through the ray of light near the outer edge of the disk. The calculation of the distribution of particle sizes according to proportions in volume is carried out by means of the software logic program of CPS measuring devices with the aid of the Mie theory. For this. the complex refractive index of the pigment is needed. This was determined by an ellipsometry in pressed tablets of the powder pigment. The density, also necessary, of the pigment particles was determined with a helium gas pycnometer (AccuPyc 1330 from Micromeritics). The centrifuge, immediately before each measurement of a sample, is calibrated with a pattern of particle sizes. As a standard, a monocrystalline diamond powder (average particle diameter 0.52 µm, a very narrow particle size distribution) was used.

Application Example 1 In the AM system, greenish yellow, transparent and intense colored varnishes are obtained with the monoazoic pigment produced according to Example 1. The viscosity of the varnish is low, the brightness is high. In comparison with a pigment that had been produced in accordance with EP-A-0 894 831, Example 1, the chromatic strength is essentially higher and the full hue is essentially more transparent.

Application example 2 Test method for chromatic filters Production of a chromatic test filter: A chromatic filter paste is first produced, which is composed of a pigment composition, binding agents, solvents and dispersion aids according to the following recipe: 77% by weight of 1-methoxy-2-propyl acetate 10% by weight of a styrene and acrylic polymer 10% by weight of a pigment; Y

3% by weight of a dispersing aid agent.

The preceding mixture is dispersed with zirconium balls (Ø (= diameter) 0.5-0.7 mm) in a paint shaker (in English paint shaker) for 2 hours. The dispersion is then filtered. The chromatic filter paste obtained in this way is applied to a glass substrate by means of a centrifugal coating device (in English Spin Coater) in order to produce a color filter film (Color Filter-Film). Transparency, color values, heat resistance and contrast are determined in this chromatic filter film. The transmission of the coated glass substrate is determined by a spectrophotometry in the range of use of 400-700 nm. The color values are described with the CIE color triangle (values of xyY: x describes in this case the blue-red axis, and describes the blue-green axis and Y describes the brightness.

The viscosity is determined in the chromatic filter paste described above with a rotary viscometer at a temperature of 23 ° C ± 0.5 ° C and at a shear rate of 60 s-1.

The heat resistance is described by the delta E value; the delta E value is determined according to DIN 6174, it describes the total distance between colors and can be calculated from the values of x, y,

Y. The coated glass substrate, after a transmission measurement, is tempered at 80 ° C for 10 min (minutes). The transmission is then measured and the delta E value is calculated. The coated glass substrate is then tempered at 250 ° C for 1 h (hour) and again a delta E value is determined. In addition, with the chromatic filter paste Full-color varnishing is produced and after dilution with a white paste, a so-called rinse varnishing is produced using a scraper application, whose color characteristics are evaluated. The test for a chromatic filter with the pigment produced according to Example 1 is as follows: A chromatic filter paste is produced. The viscosity of the chromatic filter paste is: η = 7 mPa s. Next, 3 ml of the chromatic filter paste is added with a pipette and applied on a glass substrate by means of a centrifugal coating apparatus with a rotation speed of 2,500 rpm (revolutions per minute) for 20 s (seconds). The color properties of the chromatic filter film are then determined by a spectrophotometry.

Color values: Transmission values:

x

Y Y

0.399

0.448 83.66

Wavelength

400 nm 410 nm 420 nm 430 nm 440 nm 450 nm

Transmission (%)

2.5 3.6 5.7 9.2 14.4 22.0

Wavelength

460 nm 470 nm 480 nm 490 nm 500 nm

Transmission (%)

32.7 43.4 56.5 68.3 77.2

Wavelength

510 nm 520 nm 530 nm 540 nm 550 nm 560 nm

Transmission (%)

82.9 86.2 88.1 89.2 89.7 89.7

Wavelength

570 nm 580 nm 590 nm 600 nm 610 nm

Transmission (%)

89.5 89.2 89 88.8 88.8

Wavelength

620 nm 630 nm 640 nm 650 nm 660 nm 670 nm

Transmission (%)

88.9 89 89.4 89.8 90.3 90.7

Wavelength

680 nm 690 nm 700 nm

Transmission (%)

91.0 91.2 91.3

Stability against heat is good.

5 The varnishes show a high transparency and intensity of color and a pure color tone.

Application example 3 Production of coloring agent preparations for inkjet printing: The pigment is filled in a deionized water in common with the dispersing agents mentioned below, with the organic solvent and with the other additives and then homogenized and dispersed previously

10 with a solvent apparatus. Subsequent fine dispersion is carried out with the help of a pearl mill, grinding being carried out by cooling until the desired particle size distribution of the pigment particles is achieved. Thereafter, the dispersion is adjusted with a deionized water to the desired final concentration of the pigment.

The coloring agent preparation described in the following Example, was produced in accordance with the procedure described above, the following components being used in the amounts indicated, such that 100 parts of the coloring agent preparation result, and the parts They mean parts by weight.

Preparation of coloring agent 1 for inkjet printing: 20 parts of the pigment, produced according to Example 1 2.5 parts of an acrylate resin, Na salt (dispersing agent)

20 1.2 parts of an alkyl ether of poly (ethylene glycol), Na salt (dispersing agent) 7.5 parts of propylene glycol 0.2 parts of a preservative the rest water

Testing of the technical properties for printing the preparation of coloring agent: ____________________________________________________________________________________________

In order to assess the technical properties for printing, a test ink was produced from the previous preparation of coloring agent 1 and its printability was investigated with a thermal inkjet printer.

For the production of the test ink, the preparation of coloring agent 1 was finely filtered first through a 1 µm filter, in order to separate the abrasion-worn material from the grinding bodies and

30 the eventual thick portions. After this, the preparation of the filtered coloring agent was diluted with water and met with other low molecular weight alcohols and polyols, the pigment content being adjusted to 5% by weight, based on the ink (100% by weight). With the HP 960C (Hewlett Packard) printer, test images were printed on normal commercial papers (copier papers) and special (premium quality) papers from Hewlett

35 Packard. The evaluation regarding the quality and superiority of the printed image was carried out by visual observation.

The test ink produced from the preparation of coloring agent showed in this case a very good printing behavior. In particular, high reliability of the test ink was established in the course of printing (very good incipient printing behavior, no clogging of the nozzles)

40 and a very uniform printed image of excellent quality on the different papers used.

Claims (7)

1.- Monoazoic pigment of the formula (I) in the beta crystalline phase image 1 characterized in that at least 90% by weight of the particles have an equivalent Stokes 5 diameter less than or equal to 130 nm. 2. Monoazo pigment according to claim 1, characterized in that at least 90% by weight of the particles have an equivalent Stokes diameter less than or equal to 100 nm. 3. Monoazo pigment according to claim 1 or 2, characterized in that the contrast ratio C = Ys / Yw is less than or equal to 0.22. 4. Monoazoic pigment according to one or more of claims 1 to 3, characterized in that the contrast ratio C = Ys / Yw is less than or equal to 0.20. 5. Process for the production of a monoazoic pigment according to one or more of claims 1 to 4, characterized in that a monoazoic pigment of the formula (I) in the alpha crystalline phase is subjected to a kneading in a salt. Method according to claim 5, characterized in that the monoazoic pigment of the formula (I) in the alpha crystalline phase is kneaded with an organic liquid and with a crystalline salt, in the form of a very viscous and kneadable paste. 7. Method according to claim 6, characterized in that the organic liquid is chosen from the group of glycols, glycol ethers, dimethylformamide, N-methyl-pyrrolidone and dimethylsulfoxide. Method according to claim 6 or 7, characterized in that the organic liquid is di (ethylene glycol). 9. Use of a monoazoic pigment according to one or more of claims 1 to 4 for the pigmentation of high molecular weight organic materials of natural or synthetic origin, as well as electrophotographic toners and developers, electret materials, chromatic filters , inks, printing inks and seeds. 10. A high molecular weight organic material, containing a coloristically effective amount of the monoazo pigment according to one or more of claims 1 to 4. 11. Chromatic filter, which contains a coloristically effective amount of the monoazoic pigment according to one or more of claims 1 to 4.