MXPA00007035A - Aqueous pigment preparations - Google Patents

Abstract

Aqueous pigment preparations containing a) at least one pigment, b) at least one condensation product based on A) suphonated aromatics, B) aldehydes and/or ketones and optionally C) one or several compounds selected from the group of non sulphonated aromatics, urea and urea derivatives, and c) at least one polyether polyol with a boiling point of above 150°C, especially above 250°C, at normal pressure. The inventive preparations are highly suitable for pigmenting natural or synthetic materials.

Description

AQUEOUS PREPARATIONS OF PIGMENTS.

Field of the invention. The invention relates to aqueous preparations of pigments, to a process for their preparation as well as to their use for the pigmenting of natural and synthetic materials.

Background of the Invention Aqueous pigment preparations are already known from the prior art such as for example in DE-A 3 231 299, EP-A 816 406 as well as DE-A 41 25 458. However, these pigment preparations have still certain drawbacks for its industrial application.

Detailed description of the invention. The present invention relates to novel aqueous preparations of pigments containing a) at least one pigment, b) at least one condensation product based on A) sulfonated aromatics, B) aldehydes and / or ketones and, if appropriate, REF .: 121726 C) one or more compounds, selected from the group of unsulfonated aromatics, ureas and urea derivatives and c) at least one polyether polyol with a boiling point at a normal pressure higher than 150 ° C, especially higher than 250 ° C. The pigments of the pigment preparations according to the invention are not subject to any limitation. These can be organic or inorganic in nature. Suitable inorganic pigments of component a) are, for example, oxide type pigments such as iron oxides, titanium dioxide, nickel oxides, chromium and cobalt blue oxides as well as zinc sulphides, ultramarine, sulphides of the earths rare, bismuth vanadate as well as soot, soot being considered as pigment in the scope of this application. Particular mention should be made of acid soils up to alkaline in the process of soot gas or soot from furnaces as well as chemically modified surface soot, for example soot containing sulfo or carboxyl groups.

Suitable organic pigments are, for example, those of the monoazo, diazo, varnished azo, β-naphthol, naphthol AS, benzimidazolone, diazo-condensation, azo-metal complex, isoindolinone and isoindoline series, as well as polycyclic pigments, for example from the phthalocyanine series , quinacridone, perylene, perinone, thioindigo, anthraquinone, dioxazine, quinophthalone and diketopyrrolopyrrole. Mixed crystallites (solid solutions of the mentioned pigments), mixtures of organic and / or inorganic pigments, with organic and / or inorganic pigments such as for example metallic, mica or talc pigments coated with soot, for example mica, are also suitable. coated with iron oxide in the CVD process (layered silicate) as well as mixtures of the mentioned pigments with each other. In addition, varnishes such as Ca, Mg and Al varnishes of dyes containing sulfonic groups and / or carboxylic groups should be mentioned. Particularly preferred pigments from the group of metallic azo-complex pigments are pigments of the formula (III) or their tautomeric forms where R1, R2, R3 and R4, independently of each other, mean hydrogen, alkyl, especially alkyl having 1 to 6 carbon atoms, cycloalkyl, especially cycloalkyl with 5 to 8 carbon atoms, aryl, especially phenyl, optionally substituted, aralkyl , especially aryl with 6 to 10 carbon atoms-alkyl having 1 to 4 carbon atoms, such as benzyl or ethyl-phenyl, or hetaryl, Z1 to Z4, independently of one another, signify O or NR5 and R5 signifies hydrogen or cyano.

Particularly preferred pigments of the formula (III) correspond to the formulas (VIII) and (IX) especially in the form of their occlusion compounds or intercalation compounds, the occlusion compound preferably being a cyclic or acyclic compound, preferably carboxylic acid amides or sulphonic acid amides, urea or substituted ureas as well as heterocycles, especially 2,4, 6-triamino-l, 3, 5-triazine, acetoguanamine and benzoguanamine.

As salts and complexes of the compounds of the formula (III), preference is given to the salts and complexes of the mono-, di-, tri- and tetraanions with the metals Li, Cs, Mg, Cd, Co, Al, Cr, Sn, Pb, particularly preferably Na, K, Ca, Sr, Ba, Zn, Fe, Ni, Cu , Mn. Nickel salts or nickel complexes and their solid solutions, intercalation and occlusion compounds, have a special meaning. Particular preference is given to an occlusion compound, intercalation compound, solid solution of a salt or a complex of azobarbital acid, especially preferably a complex of azobarbituric acid-nickel-1: 1.

Condensation product of component b): Based on means that the condensation product has been obtained, if appropriate, from other reagents in addition to A, B and, if appropriate, C. Preferably, condensation products will be prepared in the field of the application however only from A, B and, if appropriate, C. As sulphonated aromatics of component A), fumylated sulphonates will also be understood within the scope of this application. Preferred sulphonated aromatics are: naphthalenesulfonic acids, phenolsulfonic acids, dihydroxybenzenesulfonic acids, sulfonated dithioethers, 4, -dihydroxydiphenylsulfone sulfomethylated, sulfonated diphenylmethane, sulfonated biphenyl, sulfonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulfonated terphenyl or benzenesulonic acids. Suitable aldehydes and / or ketones of component B) are especially aliphatic, cycloaliphatic as well as aromatic. Aliphatic aldehydes are preferred, with formaldehyde as well as other aliphatic aldehydes having 3 to 5 carbon atoms being particularly preferred. Suitable non-sulfonated aromatics of component C) are, for example, phenol, cresol, 4,4'-dihydroxydiphenylsulphone or dihydroxydiphenylmethane. Suitable urea derivatives are, for example, dimethylolurea, melamine or guanidine. As the preferred condensation product of component b), one based on A) at least one sulfonated aromeate, selected from the group consisting of naphthalenesulfonic acids, phenolsulfonic acids, acids, is used dihydroxybenzenesulfonic acids, sulphonated dithioethers, 4-dihydroxydiphenylsulphone sulfonated sulfonate, sulfonated diphenylmethane, sulfonated biphenyl, sulphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulfonated terphenyl and benzenesulfonic acids, B) formaldehyde and, optionally C) one or more compounds, selected from the group consisting of group consisting of phenol, cresol, 4,4'-dihydro-idyphenylsulfone, dihydro-idyphenylmethane, urea, dimethylolurea, melamine and guanidine The condensation product obtained preferably during condensation preferably has a mean degree of condensation of 1 to 150, particularly preferred from 1 to 20, especially from 1 to 5. The condensation products of component b) can be used in the form of an aqueous solution or suspension or as a solid product, for example in the form of powder or granules, preferably in the form of a spray-dried or granular powder. The preferred condensation products of component b) have an inorganic salt content of less than 10% by weight, preferably less than 5% by weight, especially less than 1% by weight, based on the solution or the aqueous suspension used for the components or in relation to the solid product used in component b). It is also preferred to use condensation products of component b) which are low in residual monomers up to and including residual monomers. "Monomer poor" means a monomer residual content of less than 30% by weight, preferably less than 20% by weight, based on the condensation product, in particular less than 10% by weight, preferably less than 5% by weight. % in weigh. The residual monomers in this context will be understood as the reagents used for obtaining the condensation product. Such condensation products which are poor in salts and poor in residuals are known, for example, from EP-A 816 406. The condensation products of component b) can be prepared, for example, by first obtaining the sulfonated aromatics of component A) optionally in a mixture with the unsulfonated aromatics of component C) by reaction of the aromatics in which they are based on a sulfonating agent, preferably sulfuric acid, especially concentrated sulfuric acid, chlorosulphonic acid, atidosulphonic acid or oleum. Preferably they will be used, relative to one mole of the aromatics on which component A) is based, from 0.4 to 3.2 moles, especially from 0.8 to 1.6 moles of sulphonation agent. The condensation is then carried out with aldehydes and / or ketones of component B), preferably formaldehyde, optionally together with other compounds of component C). The condensation is preferably carried out in aqueous solution at a pH value of from 0 to 9. In this case, it is preferably used per mole of sulfonated aramid A) or per mole of a mixture formed by sulfonated aromatics of component A) and unsulfonated aromatics of component C), from 0.4 to 1.5 moles, especially from 0.4 to 1.0 moles of component B). The neutralization of the sulfonic condensation product of component b) with a base is then carried out, if appropriate. The separation of the inorganic acids or their salts as well as the reduction of the residual monomer content can be carried out, for example, by means of membrane separation processes. Suitable methods of separation by preferred membranes are ultrafiltration, diffusion dialysis or electrodialysis. The membranes used in membrane separation processes or in ultrafiltration have, in a preferred embodiment, a barrier for molecular weights (MWCO) of 1000 to 50,000 Daltons. The separation of the inorganic acids with the aid of a membrane separation process is preferably carried out by diafiltration with acid-stable ultrafiltration or nanofiltration membranes according to the cross-current filtration form. Suitable membranes include, for example, polyhydantoin membranes such as those known from EP-A 65 20 44.

Preferred membranes for this purpose have a MWCO level of 2,000 to 20,000 Daltons. If necessary, a simultaneous concentration is carried out during this stage of the process. The invention also relates to novel preparations containing at least one condensation product b1) based on 4,4'-dihydroxydiphenylsulphone, sulfonated dithioethers and formaldehyde; 4, '-dihydroxydiphenylsulfone, phenolsulfonic acid and formaldehyde; , 4 '-dihydroxydiphenyl-sulfone, sodium bisulfite, formaldehyde and urea; Naphthalenesulfonic acid, 4, '-dihydroxydiphenylsulfone and formaldehyde; sulfonated terphenyl and formaldehyde; and / or sulfonated 2-hydroxybiphenyl and formaldehyde. These preparations according to the invention of the condensation products b) have an inorganic salt content of less than 10% by weight, in particular less than 5% by weight, particularly preferably less than 1% by weight, based on the preparation . In addition, the condensation product bl) has condensation from 1 to 150, preferably from 1 to 20, especially less than or equal to 5, preferably from 1 to 5.

The preparation according to the invention containing the condensation product b) preferably has a residual monomer content of less than 30% by weight, preferably less than 20% by weight, especially less than 10% by weight, particularly preferably less than 5% by weight, based on the condensation product bl). These preparations according to the invention are preferably obtained by preparation of condensation b) and then treatment by membrane technology and optionally drying. Membrane separation processes include those mentioned above. In principle, the process parameters known from EP-A 816 406 can be used. The preparation containing the component b) can be used, for example, in the form of an aqueous solution or suspension or as a solid product, for example in the form of powder or granules, preferably in the form of powder sprayed or granulated. The preparation containing component bl) is preferably used as component b) of the aqueous preparations of pigments according to the invention. The invention also relates to the use of the preparation containing the condensation product b1) according to the invention as a tanning agent, blenders, auxiliary drilling agents or dispersing agents. The use of the preparations according to the invention or the preparations obtained according to the invention, in the form of dispersants, are preferably characterized in that the preparation according to the invention or the preparation obtained according to the invention is added a. an aqueous suspension of a solid product, in particular of a pigment, preferably organic pigment, and / or dye and / or optical brightener and / or plant protection agent and the suspension is homogenized, if appropriate, for example in a comminution device wet such as a pearl mill. In this case, for example, dispersions stable to low viscosity storage are obtained, which, if appropriate, are spray dried.

In order to obtain the preferred preparations according to the invention, one or more preparations according to the invention are applied to the surface of the pigments. This can be verified, for example, during or after the synthesis of the pigments, in a finishing process, or during the incorporation of the pigment in an application medium or during the manufacture of the pigment preparation according to the invention as described previously. The use of the preparations according to the invention or obtained according to the invention as blenders, in particular as concrete blenders or auxiliary drilling agents, is preferably characterized in that the preparation according to the invention or the preparation obtained according to the invention is added to a suspension or solid product to be liquefied, preferably in an amount of 0.1 to 1.0% by weight, based on the suspension to be liquefied, if appropriate together with water. The use of the preparations according to the invention or of the preparations obtained according to the invention as tanning agents is preferably characterized in that a tanned leather, for example chrome tanned leather (wet blue), is neutralized in the presence of the preparation according to the invention. or of the preparation obtained according to the invention, it is subjected to a recourse, dyed and / or greased. Usually these process steps are combined under the expression "retannage". Suitable polyether polyol components c) are preferably block homo-, co- or co-polyether polyols which are preferably prepared by reaction of ethylene oxide and / or propylene oxide with water or with low molecular weight alcohols, which have the less two hydroxy groups, such as, for example, ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,4-butanediol, hexanediol, glycerin or pentaerythritol or with low molecular weight amines carrying at least two amino groups with reactive hydrogen atoms, such as ethylenediamine or diethylenetriamine. Preferred polyether polyols are polyalkylene glycols having an average molecular weight, determined as the number average, of from 200 to 11,000 g / mol, especially from 200 to 4000, particularly preferably from 250 to 1000. Polyethylene glycols and / are particularly preferred. or polypropylene glycols, especially polyethylene glycols with an average molecular weight of 200 to 800 g / mol as well as tripropylene glycol. Preferred pigment preparations according to the invention contain from 2 to 70, in particular from 10 to 50,% by weight of pigment of component a), in particular organic pigment, based on the preparation, of from 0.1 to 120, in particular from 0.2 to 60. % by weight of the condensation product of component b), based on the pigment of component a), from 1 to 30, preferably from 2 to 20% by weight of polyether polyol of component c), based on the preparation as well as, from 29 to 97% by weight of water, based on the preparation.

The preferred amounts of the condensation product b) amount to 0.2 to 10, especially 0.5 to 6 mg / m2, based on the specific surface of the pigments (B.E.T.) of component a). The specific surface area can be determined, for example, according to the so-called BET method. The preparation of pigments according to the invention can also contain other additives. Particularly preferably, it contains, in the form of other components d), a nonionic or anionic dispersing agent selected from the group consisting of: di) esters of sulfosuccinic acid, alkylbenzene sulphonates and alcohols of sulfated fatty acids, alkoxylates or their salts and / or d2) lignin sulphonates according to the sulphite process or according to the Kraft process and / or d3) oxyalkylation products and / or their esters, which are obtained from styrenes, optionally substituted, on phenols, optionally substituted and reaction with ethylene oxide and / or ethylene oxide and / or propylene oxide. Suitable alkoxylated fatty acid alcohols of the di) component are those alcohols of fatty acids having 6 to 22 carbon atoms endowed with 5 to 120, preferably 5 to 60, especially 5 to 30, ethylene oxide, which are saturated or unsaturated, especially teari 1-alcohol. Especially preferred is an alkoxylated tearyl alcohol with 8 to 10 ethylene oxide units. The sulphonated alkoxylated fatty acid alcohols are preferably present as salts, especially as alkali or amine salts, preferably as diethylamine salts. Suitable ligninsulfonates of component d2) are those obtained according to the sulphite or Kraft process. Preferably they are products that are partially hydrolyzed, oxidized, propoxylated, sulphonated, sulfolated or desulphonated and which are fractionated according to known processes, for example according to the molecular weight or according to the degree of sulfonation. Mixtures consisting of lignin sulphites and Kraft are also perfectly effective. Ligninanosulfonates having an average molecular weight of between 1,000 and 100,000, an active lignin sulfonate content of at least 80% and preferably a low polyvalent cation content are particularly suitable. The degree of sulfonation can vary within wide limits. Preferred dispersants of component d3) are compounds of formula (I) and / or (II), such as those known, for example, from DE-A 197 12 486, wherein R15 means hydrogen or alkyl having 1 to 4 carbon atoms, R16 means hydrogen or CH3, R17 means hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkoxycarbonyl having 1 to 4 atoms carbon or phenyl, m means a number from 1 to 4, n means a number from 6 to 120, R18 is the same or different for each unit with the index n, and means hydrogen, CH3 or phenyl, verifying itself, in the case of the concomitant presence of CH3 in the various groups - (- CH2- CH (R18) -0 -) - by 0 to 60% of the total value of n, that R18 means CH3 and by 10 to 40% of the value total of n, that R means hydrogen and, in the case of the concomitant presence of phenyl in the various groups - (- CH2-CH (R18) -0-) -, at 0 to 40% of the total value of n, that R18 means phenyl and at 10 to 60% of the total value of n, that R18 means hydrogen.

Esters of alkoxylation products (I) of the formula (II) wherein R15 ', R16', R17 ', R18', m 'and n' take the range of meanings of R15, R16, R17, R18, m respectively n, however independently thereof, X means the groups -S03 ~, -S02 ~, -P03 ~ "or -CO- (R19) - COO", Kat means a cation chosen from the group consisting of H +, Li +, Na +, K +, NH4 + or H0-CH2CH2-NH3 +, two cations being present in the case where X = -P03 and R19 means a divalent aliphatic or aromatic moiety, preferably represents alkylene with 1 to 4 carbon atoms, especially ethylene, moieties with 2 to 4 monounsaturated carbon atoms, especially optionally acetylene or phenylene, especially ortho-phenylene, optionally substituents being preferably alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms or phenyl. The preferred forms cited in DE-A 197 12 486 of these two compounds (I) and (II) are also an integral part of this application. As other components e), for example, polymeric dispersing agents can be used. As such, for example, the compounds cited in the "Water-Soluble Synthetic Polymers: Properties and Behavior" catalog (Volume I + II by Philip Molyneux, CRC Press, Florida 1983/84) should be considered.

Other polymeric dispersing agents are, for example, water-soluble as well as water-emulsifiable compounds, for example homo- and copolymers, graft copolymers and graft copolymers as well as statistical block copolymers. Particularly preferred polymeric dispersing agents are, for example, block copolymers AB, BAB and ABC. In block copolymers AB or BAB, segment A is a hydrophobic homopolymer or copolymer, which ensures a bond with the pigment and block B is a hydrophilic homopolymer or copolymer or a salt thereof and ensures the dispersion of the pigment in medium aqueous. Such polymeric dispersing agents and their synthesis are known, for example, from EP-A-518 225 as well as from EP-A-556 649. Further examples of suitable polymeric dispersing agents are polyethylene oxides, polypropylene oxides, polyoxymethylenes, polytrimethylene oxides, polyvinyl methyl ethers, polyethylene imines, polyacrylic acids, polyarylamides, polymethacrylic acids, polyethacrylamides, poly-N, N-dimethyl-acrylamides, poly-N-isopropylacrylamides, poly-N-acrylglycinamides, poly-N-methacrylglycinamides, polyvinyl alcohols, polyvinyl acetates, polyvinylalcohol copolymers and polyvinyl acetates, polyvinyl pyrrolidone, polyvinyloxazolidones, poly inylmethyloxoxolidones. Furthermore, natural polymeric dispersing agents such as cellulose, starches, gelatins or their derivatives as polymeric dispersing agents have significance. Polymers made up of amino acid units, for example polylysine, polyaspartic acid, etc. are particularly suitable. As other anionic dispersing agents, there may be mentioned, for example: alkylsulfates, ether sulfates, ethercarboxylates, phosphate esters, sulfosuccinate amides, paraffinsulfonates, olefin sulfonates, sarcosinates , isethionates and taurates Component d) is preferably used in an amount of 0.1 to 100%, especially 0.1 to 60% by weight, based on the pigment of component a). Preferably they will be used in an amount of 0.1 coarse 8, especially 0.1 to 4 mg / m2, based on the specific surface (determined according to the method called B.E.T for example by adsorbing N2 on powder pigment) of the pigment of component a). In addition, the pigment preparations can contain other customary additives for preparations of this type, such as, for example, nonionic or anionic humectants, inorganic or organic thickeners or thixotropic agents as well as preservatives. Preservative agents should be understood, for example, as isothiazolinones, for example 1,2-benzisothiazole-3- (2H) -one, chloro-2-methyl-4-isothiazolin-3-one or 2-methyl-4-iso-thiazolinone. 3-one, pentachlorophenolsodium, 1, 3, 5-triethylolhexahydro-s-triazine or mixtures thereof, which are generally used in an amount of 0 to 1% by weight, preferably 0.05 to 0.5% by weight, especially from 0.0001 to 0.2% by weight, based on the preparation. The invention also relates to a process for preparing the pigment preparations according to the invention, characterized in that the individual components of the preparations are homogenized with water in devices for wet comminution. In this case, the pigment of component a is preferably whipped, for example in the form of powder or granulate or as an aqueous suspension, for example as a presscake moistened with water, together with at least a part of the components b) and c) as well as, if appropriate, d) and / or e), if appropriate, other additives and water, preferably deionized water, to give a homogeneous grinding suspension, for example bowl with agitator mechanism or dissolver for example as a comminution device in wet if necessary in combination with a previous comminution, that is to say that they are introduced and homogenized. The grinding suspension may also contain parts of low viscosity solvents (boiling point lower than 150 ° C), which can be removed by evaporation in the course of subsequent fine grinding. However, it can also contain portions of high-boiling solvents or other additives, such as those described above, for example grinding aids or wetting agents, thickening agents. Wet grinding covers both pre-grinding as well as grinding. fine grinding. Preferably, the concentration of the pigment in the suspension is in this case above the desired concentration of the finished pigment preparation. The desired concentration of pigment is preferably adjusted after wet comminution. After the preliminary comminution, grinding is carried out up to the desired fine particle distribution. For this milling, devices such as, for example, kneaders, roller banks, kneader spindles, ball mills, rotor-stator mills, dissolvers, mills with corundum discs, vibrating mills and, especially, ball mills with stirring device, are suitable. with a high number of revolutions, loaded continuously or discontinuously with grinding bodies with a diameter of 0.1 to 5 m. The grinding bodies may in this case consist of glass, ceramic or metal, for example steel. The temperature of the grinding is preferably in the range from 0 to 250 ° C, as a rule, however below 70 ° C, especially below the cloud point of the dispersing agent used of components b) and, if necessary , d) and, if applicable, other surfactants and if necessary used. In an equally preferred manner, grinding can be carried out partially or completely in a high-pressure homogenizer or in a so-called jet disperser (known from DE-A 19 536 845), thereby reducing it to a minimum or else the content of particles detached by friction of the grinding body in the suspension or the release of soluble products from the grinding bodies (for example ions from the glass bodies) can be completely avoided. A final adjustment of the preparation of the pigments is carried out to the desired pigment concentration, preferably after grinding by adding, if necessary, an additional amount of water, if appropriate residual dispersing agent of the components b) or d) ) oe) and, if appropriate, an additional amount of polyetherpolyol of component c) as well as, if appropriate, other additives such as, for example, preservatives. In this case, the preparation of pigments according to the invention is preferably adjusted to a pH value of 5 to 9, in particular 6 to 8. After wet comminution and, if necessary, adjustment, the pigment preparations can be processed. in a powder or granulate also by means of drying, for example by spray drying. The object of the invention is also the use of the preparation of pigments for pigmenting and coloring natural and synthetic materials. Due to its special poor foam, to the excellent fine distribution, in combination with a high intensity of color and gloss, good coloristic (especially in the case of organic pigments as well as excellent rheological properties and very good storage stability) , the pigment preparations according to the invention can be used in particular for the production of aqueous dispersion and printing paints and aqueous coating systems (for example, industrial and building varnishes).

In particular, they are suitable for "inking dough paper, for painting by paper brush and for inking non-woven articles and sheets." The pigment preparations according to the invention show a very good compatibility (stability to flocculation). when they are used in aqueous polyacrylate, polyester and polyurethane systems, good mixing ability and good rheological behavior, high color intensities and very good color properties, especially brightness, are especially suitable for inking, and must also be understood this expression is the nuanced, of the various brush paints or white dispersion plasters, which are presented in practice, usually containing Ti02 and / or BaS04, the bases of which may be, for example, modified polyvinyl acetates, (poly) acrylates or (poly) is styrene-acrylate or latex, it can be incorporated easily and without flocculation in p white heels applicable to brush for exteriors commercially available and, when applied and when applied to brushes, provide perfect paint with high intensity of color and brightness. The use of the pigment preparations according to the invention in aqueous binder systems (for example dispersion paint systems, dispersion plasters, printing, varnishes and coatings) is preferably characterized in that the amounts of the pigment preparations according to the invention, necessary for the adjustment of the hue of the color, or of the mixed hue of the color, and of the intensity of the color, in the aqueous system of the binder, in which they can be finely dispersed if necessary Ti02, BaS04 or other inorganic colored or white pigments, for example by hand or mechanically, for example by means of devices with stirring devices, and are distributed homogeneously, optionally together with other customary additives, and the coating is carried out of the various substrates by means of generally known processes, such as, for example, brush application, by means of a gun, r odillo, scraper, immersion.

Furthermore, the pigment preparations according to the invention are very well suited for printing inks for inkjet printing. Ink jet printing is known per se and is generally carried out in such a way that the printing ink is charged into a receiving container of an ink jet printing head and sprayed into small droplets on the substrate. The expulsion of the ink in the form of droplets is carried out in this case, preferably, by means of a piezoelectric crystal, a heated cannula (bubbling process or thermo jet) or mechanical increase of the pressure, by exerting pressure on the ink system and in this way droplets of ink are ejected. In this case, the droplets are fired from one or more small nozzles, specifically on the substrate, such as for example paper, wood, textiles, synthetic material or metals. By means of the electronic control the individual droplets on the substrate are combined to form printing signs or graphic drawings. A process is also possible in which minimum volumes in the form of drops are applied on a substrate by means of an electrostatic deflection from a jet. from ink. In particular, the pigment preparations according to the invention are suitable for inking, whereby also the application of shades, of mass paper, inks for brush-painting of paper as well as non-woven articles and sheets, for example acetate sheets, is understood. of cellulose The mass paper inking is especially characterized in that, in a first step, for example, cellulose or a mixture of cellulose is admixed, together with water, usual fillers such as for example, inorganic white pigments, calcium carbonate, kaolin, the pigment preparations according to the invention as well as, if appropriate, customary auxiliary agents such as, for example, sizing agents, wet-setting agents, defoamers, in a suitable device, such as the so-called Dutch, pulpers or mixing containers with sufficient turbulence, then (step 2) the product mixture is further diluted by the addition of water, optionally any other customary auxiliaries such as, for example, agents for wet fixation , retention agents, agents for adjusting the pH value and then (step 3) the product mixture, obtained in this way, is fed to the feed of products from a paper machine, in which the formation of the leaves and drying to give the desired paper. The addition of the pigment preparation according to the invention can also be carried out after step 1 in the mixing vessel or in combination with step 2. In this case, the pigment preparations according to the invention are characterized by excellent performance to the retention (high color rendering) and low tendency to foaming during the manufacturing process. Even in the case of high proportions of inking greater than 10% by weight of the pigment preparations, referred to cellulose, the tendency to foaming is so small that the use of defoamers can be reduced to a minimum.

The pigment preparations according to the invention have excellent dispersion properties and distribution in hydrophilic media.

They also have a very low tendency to initial drying and drying in and on the drum.

Example 1. 0.95 moles of 4,4'-dihydroxydiphenylsulfone and 1.7 moles of sulfonated ditolylether were condensed in aqueous solution with 1.4 moles of formaldehyde. The product of the condensation was subjected to a filtration by transverse current at a transmembrane pressure of 40 bar and at a temperature of 55 ° C. In this case spirally wound membranes with a MWCO level of 3,500 g / mol were used. By means of triple continuous diafiltration, the content of sulfuric acid was reduced to a proportion of less than 0.2% by weight. At a subsequent concentration the active product content was increased by 60%. The content of residual monomers (4,4'-dihydroxydisulfone), based on the total amount of the condensation product, was reduced from 15 to 8% by weight in this case.

Example 2 Mole of phenolsulfonic acid and 3 moles of 4,4'-dihydroxydiphenylsulfone were condensed in aqueous solution at pH 8 with 2.4 moles of formaldehyde. The product of the condensation was subjected to a filtration with transverse current at a transmembrane pressure of 40 bars and at a temperature of 55 ° C, using flat membranes with a MWCO level of 3500 g / mol in a plate module. By means of triple continuous diafiltration, the sulfate content was reduced to a proportion of less than 0.2% by weight. The residual monomer content (4,4'-dihydroxydiphenylsulfone + phenolsulfonic) was reduced in this case from 14 to 7% by weight.

Example 3. 1 mol of 4,4'-dihydroxydiphenylsulphone with 1.2 mol of sodium bisulfite and 2.3 mol of formaldehyde was sulfomethylated, the product obtained was adjusted to pH 5 with sulfuric acid and further condensed with 1.5 mol. of urea and with other 0.65 moles of formaldehyde. The product of the condensation was then subjected to a filtration with transverse current at a transmembrane pressure of 35 bar and at a temperature of 35 ° C by means of a tubular membrane with a MWCO level of 2,000 g / mol. By triple discontinuous diafiltration the sulfate content was reduced to a proportion less than 0.2% by weight.

Example . One mole of naphthalene was subjected to sulfonation with 1.36 moles of sulfuric acid for about 3 hours at about 145 ° C and the sulfonation mixture obtained was condensed for about 3 hours with 1 mole of formaldehyde at 120 ° C, cooled at 50 ° C. C about 'and adjusted to pH 6 to 7 with sodium hydroxide solution. The solution was then subjected, at 50 ° C, and with an inlet pressure in the 30 bar module, to a filtration with transverse current, using a flat membrane as a membrane cushion with a MWCO level of 3,500 g / mol. By triple diafiltration the sulfate content was reduced from 11.5% by weight to a proportion of less than 0.2% by weight. The residual monomer content, based on the total amount of the condensation product, was reduced from 5 to 1% by weight in this case.

Example 5. Acidic condensate 0.66 moles of 4,4'-dihydroxydiphenylsulphone and 0.93 moles of naphthalenesulfonic acid with 0.82 moles of formaldehyde were condensed. The solution of the condensation was subjected to 50 ° C and an inlet pressure in the 30 bar module, to a cross-current filtration, using spirally wound membranes with a MWCO level of 8000 g / mol. By double diafiltration the content of sulfuric acid was reduced from 4 to less than 0.2% by weight. The residual monomer content, based on the total amount of the condensation product, decreased from 37 to 19% by weight in this case.

EXAMPLE 6 1 mol of industrial terphenyl or a mixture of terphenyl-diphenyl and 3 mol of sulfuric acid were sulphonated, the sulfonation mixture obtained was condensed with 0.67 mol of formaldehyde and neutralized with sodium hydroxide solution. The product was spray dried.

Example 7. 0.38 moles of 4,4'-dihydroxydiphenylsulfone were mixed with naphthalene-β-sulfonic acid, prepared from 1 mole of naphthalene and 1.43 moles of sulfuric acid, and condensed with 0.7 moles of aqueous formaldehyde, it was adjusted to a pH of about 3.5 with sodium hydroxide solution and dried in the dryer by spraying.

Example 8. 1 mol of dithylether isomer mixture was subjected to sulfonation with 2 mol of sulfuric acid and the obtained mixture of ditolylether sulfonic acids was condensed with 1 mol of 4,4'-dihydroxydiphenylsulfone in aqueous solution with 0.93 mol of formaldehyde, it was adjusted to about pH 3.5 with sodium hydroxide solution and sprayed.

Example 9 0.3 moles of 2-hydroxybiphenyl with 0.37 moles of sulfuric acid were subjected to sulfonation, condensed with 0.23 moles of formaldehyde and adjusted to pH 6 with sodium hydroxide solution and spray dried.

Example 10. Obtaining a dispersing agent according to formula (II) • In a 2 liter stirring device, nitrogen scavenging, (0.975 mol), 1061 g of tristyrylphenyloxyethylate emulsifier of the formula (I) were placed. where: 2, 7 n: 16 R2: H Ris: H R17: H and Laughs: H, with a statistical chain length of approximately 16 EO units and were combined to 85 ° C with (0.975 moles) 97.5 g of succinic acid anhydride. It was stirred, under a slight stream of nitrogen, for 3 hours at 85 ° C, whereby the suspension, initially turbid, became clear and diluted. Refrigerated at 50 ° C and filtered through a G-2 glass frit. 1,149 g of a viscous, colorless to yellowish liquid were obtained with the following properties: 1% pH value in completely desalinated water = 3.7 1% turbidity point in completely desalinated water = 45-46 ° C acid number = 47.4 mgKOH / g saponification index = 95.2-100% The mixture, obtained in this way, had more than 9% by weight of the dicarboxylic acid semi-esters according to formula (II).

And 6a. Alternatively, the solution of the condensation from Example 6 was prepared, before the addition of the sodium hydroxide solution, by means of the membrane technology as in Example 5, whereby a sulfuric acid-free preparation was obtained monomers Example 7a. Alternatively, the solution of the condensation from Example 7 was prepared, before the addition of the sodium hydroxide solution, according to the membrane technology as in Example 5, whereby a preparation free of sulfuric acid and poor in monomers Example 8a. Alternatively, the solution of the condensation from Example 8, after the addition of the sodium hydroxide solution, also at 55 ° C and with an inlet pressure in the 30 bar module, was subjected to a cross-current filtration. In this case, ultrafiltration membranes were used in the form of flat membranes (MWCO 8000 g / mol), which were mounted on a plate module. By triple diafiltration and subsequent concentration the sulfate content was reduced from 5.0 to less than 0.2%.

Example 9a. Alternatively, the condensation solution from Example 9, after addition of the sodium hydroxide solution, was also subjected to 45 ° C and with an inlet pressure in the 20 bar module, to a filtration with. transverse current. In this case, ultrafiltration membranes in the form of flat membranes (MWCO 3500 g / mol) were used in the form of a membrane cushion. By double dayfiltration and subsequent concentration the sulfate content was reduced from 5.2 to 0.3%.

Example 11. 53.6 parts by weight of deionized water were placed in a rapid laboratory stirrer and, under agitation, 8.2 parts by weight of dispersing agent (compound b, 'bl) according to example 9, 8.0 parts by weight of polyethylene glycol were introduced. with an average molecular weight of 400 g / mol (PEG 400; component c), 0.2 parts by weight of 1, 2-benzisothiazol-3- (2H) -one as a preservative agent in a homogeneous manner and completely dissolved. Then, 30 parts by weight of the pigment Color Index Pigment Blue 15: 3 (BET = 68 m "Vg) were introduced and completely homogenized, then the suspension was adjusted to a pH value of 7.0 by means of hydroxide hydroxide solution. Sodium was diluted and ground in a 1-liter laboratory bead mill using glass beads with a diameter of 0.47-0.63 mm under refrigeration for 60 minutes.A 30% blue pigment preparation was obtained with a very good flowability and storage stability, which is excellently compatible when used in aqueous systems customary in the dispersion paint and varnish systems market and characterized by a high color intensity.

The pigment preparation, obtained in this way, was diluted to a pigment concentration of 4% to be used in a printing ink for ink jet printing, the composition and the parameters of the printing ink being chosen in the manner next: Deionized water 72.7% by weight Polyethylene glycol (Mw: 800 g / mol) 9.0% by weight Preparation of 30% pigment: 13.3% by weight 2-Pyrrolidone: 5.0% by weight pH value 7.2 Surface tension > 30 mN / m Maximum particle size (plate centrifuge) < 0.2 μ, The printing ink could be printed on a commercially available ink jet printer (HP, Desk Jet ® 690 C, after replacement of the existing blue ink 'originally by the printing ink according to the invention) and provided images by printing with a high intensity of color and brightness, as well as a good solidity to water and markers.

Example 29. As described in Example 11, other advantageous, highly concentrated pigment preparations were prepared using the components indicated in Table 1. Adjustment of the pH value to the indicated value was carried out. if necessary, as a step prior to grinding by adding diluted sodium hydroxide solution or dilute sulfuric acid. The determination of the viscosity was carried out 24 hours after the preparation of the preparations in a rotating viscometer of the Haake Company, Viskotester VT 550 type, spindle E 100. The viscosity data refer to a measurement at room temperature and at a shear rate of 70 s "1. The percentage indications of the dispersing agents used (component b)) refer to the solids content of the corresponding aqueous solution.

Table 1: Composition of the pigment preparations according to the invention (example 29).

• -J ? or • t- 00 OR or Ul or to o 1) Polyethylene glycol with an average molecular weight of 400 g / mol.

Testing of the foam behavior of the pigment preparations according to the invention: Test method: 0.8 g of the pigment preparation to be tested were placed in a 100 ml glass burette and filled with 80 ml of water from the pipeline or with deionized water (noble water). The burette was then shaken 20 times horizontally by hand and the height of the foam [mm] was immediately determined after 2.5, 5 and 10 minutes.

All the pigment preparations according to the invention according to Examples 11-28 as well as 12a, 15a, 18a and 25a could be evaluated as foam-free or poor in foam. As can be seen from table 2, the height of the foam decreases rapidly above the unit of measurement, that is to say that the preparations fulfill almost always the criterion of being "poor in foam" and after 2, 5 minutes .

Table 2: Results of the behavior test a the foam. Application examples 30-38. The very good adaptation of the pigment preparations according to the invention to the dyeing of paper dough was tested according to the following procedures: a) Obtaining the raw material for the paper: In a laboratory Dutch laboratory, a mixture of products constituted by 70% by weight bleached eucalyptus cellulose 30% by weight of pine sulphate cellulose with a material density of 3% over 25 ° SR in piping water. b) Formation of the sheets and inking. 2.5 g of the above ground fibrous material were diluted in an inking beaker (1000 ml) (solid) under continuous stirring in 600 ml of water from the pipe and 30% by weight of titanium dioxide pigment (Bayertitan® R-PL-1, Bayer AG) was added, based on the solid fibrous product, as a aqueous dispersion at 10% by weight. After 10 minutes of stirring, the necessary amount of the corresponding pigment preparation (see below) necessary for the establishment of a reference depth of 12/25 (DIN 54000) and, after a stirring time of 5 minutes, 5% by weight of Nadavin® DHF, Bayer AG, was added, based on the fibrous material. If necessary, the pH value was adjusted to 6.5-7.0 after another 10 minutes. The formation of the sheets was carried out on a sheet-forming plant (Rapid-Kothen® System) and then the sheet was dried at approximately 95 ° C for about 8 minutes in the drying cabinet. The determination of the necessary quantities of each pigment preparation for a reference type depth 1/25 by means of the procedure described above through the measurement of the color intensity difference in a Macbeth Color Eye 7000 type measuring device versus a chromatically corresponding textile sample (depth reference type 1/25), whose color intensity is taken as 100%. After the determination of the amounts required for a reference depth of 1/25 of the corresponding pigment preparation, analogous staggered solutions were prepared in a laboratory paper machine according to the aforementioned recipes. These inked raw papers were tested for light fastness (DIN 54004), solidity to styrene and plasticizers (dibutyl phthalate). The evaluation was carried out after 24 hours of immersion of the inked paper strips with respect to the bleeding and eventually to the coloring of the solution. In the same way, an acid fastness test (10% sulfuric acid) and alkali solidity (10% sodium carbonate solution) was carried out by means of a drop of the corresponding solution for 1 minute. on the dyed paper, removal of the excess with filter paper and evaluation of the paper in the wet state. Evaluation of the solidity: good: + limited: +/- bad: The use of the pigment preparations according to the invention gave bright inks with a great intensity of color with excellent fastnesses. The test results of these application examples 30-38 have been brought together in table 3.

The pigment preparations according to the invention are also suitable in particular for the inking of so-called decorative laminate papers, such as those used for the manufacture of decorative layered pressed materials. For example, raw papers, manufactured according to application examples 30-38, were respectively coated with a 50% aqueous solution of melamine formaldehyde on a resin ratio of approximately 56%, subjected to a prior condensation according to a process of continuous passage for 2.5 minutes at 120 ° C to a residual moisture of about 4-6% by weight and pressed for 5 minutes at various temperatures from 150 to 180 ° C and at a pressure of 10 N / mm2 in a high pressure press to give a laminate. The formation of the laminate was constituted by: 1 pressed plate, chromed, 2 slightly pigmented support papers (embedded in melamine resin) 2 soda kraft papers (embedded in phenolic resin) 1 pigmented decorative paper according to the invention (according to the examples 30-38) 1 pressed plate, chromed. The pigmented papers according to the invention (decorative papers) could be pressed perfectly in the indicated temperature range and provided laminates with a high gloss and color intensity. No displacement of the tonalities of the color could be observed when the pressing was carried out at 150 ° C and at 180 ° C.

Application example 39: 3 parts by weight of a pigment preparation, manufactured according to example 28, were homogeneously introduced by hand over 5 minutes into 100 parts by weight of a white ink commercially available in dispersion paint (Tinova® Tácklasur , Fa Akzo Nobel) and provided a bright brush, color intense, stable to flocculation and free of mottles, which could no longer be improved through an additional mixing by means of a rapid stirrer for 3 minutes. In the same way, a 10% paint provided a picture of properties of the same quality. It is noted that in relation to this date, the best method known to the applicant, to carry out the said invention, is that which is clear from the present description of the invention. Having described the invention as above, it is claimed as property what is contained in the following:

Claims (17)

1. RE IVINDICATIONS 1. - Aqueous preparations of pigments, characterized in that they contain a) at least one pigment, b) at least one condensation product based on A) sulfonated aromatics, B) aldehydes and / or ketones and optionally C) one or more compounds, chosen from the group of sulfonated aromatics, ureas and urea derivatives and c) at least one polyethanol polyol with a boiling point at normal pressure greater than 250 ° C.
2. 2. Aqueous preparations of pigments according to claim 1, characterized in that they contain as component b) at least one condensation product based on A) at least one sulfonated aromato, chosen from the group consisting of naphthalenesulfonic acids, phenolsulonic acids, dihydroxybenzenesulfonic acids sulphonated dithioethers, sulphonated 4-dihydroxydi phenylsulfone, sulphonated diphenylmethane, sulphonated biphenyl, suphonated hydroxybiphenyl, especially 2-hydroxybiphenyl, sulfonated terphenyl and benzenesulonic acids, B) formaldehyde and, optionally C) one or more compounds, selected from the group consisting of group consisting of phenol, cresol, 4,4'-dihydroxydiphenylsulphone, dihydroxydiphenylmethane, urea, dimethylolurea, melamine and guanidine.
3. 3. Aqueous pigment preparations according to claim 1, characterized in that the condensation product of component b) has a mean degree of condensation of 1 to 150, especially 1 to 20, preferably 1 to 5. 5.- Preparations of pigments according to claim 1, characterized in that the residual monomer content of the condensation product of the components b) is less than 30% by weight, preferably less than 20% by weight, especially less than 10% by weight , referred to the condensation product. 5. Aqueous preparations of pigments according to claim 1, characterized in that they contain - from 2 to 70, especially from 10 to 50% by weight of pigment of component a), especially organic pigment, based on the preparation, - of 0.1 up to 120%, especially from 0.2 to 60% by weight of condensation product of component b), based on the pigment of component a), - from 1 to 30, preferably from 2 to 20% by weight of polyetherpolyol of component c) referred to to the preparation as well as, from 29 to 97% by weight of water, based on the preparation. 6. Aqueous preparations of pigments according to claim 1, characterized in that they contain as component c) homo-, co or co-polyether polyols block, which are prepared by reaction of ethylene oxide and / or propylene oxide with water or alcohols of low molecular weight, having at least two hydroxy groups, especially those selected from the group consisting of ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,4-butanediol, hexanediol, glycerin and pentaerythritol or with amines of low molecular weight, which carry at least two amino groups with reactive hydrogen atoms, especially those chosen from the group consisting of ethylenediamine and diethylenetriamine. 7. Aqueous preparations of pigments according to claim 1, characterized in that they also contain a nonionic or anionic dispersing agent of component d) selected from the group consisting of di-esters of sulfosuccinic acid, alkylbenzene sulphonates and alcohols of sulphated fatty acids, alkoxylates or their salts and / or d2) lignin sulfonates according to the sulphite process or according to the Kraft process and / or d3) oxyalkylation products and / or their esters, which are obtained by the addition of styrenes, optionally substituted, on phenols, optionally substituted and reaction with ethylene oxide and / or propylene oxide. 8.- Aqueous pigment preparation according to claim 1, characterized in that component a) is a pigment selected from the group consisting of azo metallic complex pigments of the formula (III) wherein R1, R2, R3 and R4, independently of one another, mean hydrogen, alkyl, especially alkyl having 1 to 6 carbon atoms, cycloalkyl, especially cycloalkyl with 5 to 8 carbon atoms, aryl, especially phenyl, optionally substituted , aralkyl, especially aryl with 6 a 10 carbon atoms-C 1 -C 4 -alkyl, such as benzyl or ethyl-phenyl, or hetaryl, Z 1 to Z i, independently of one another, signify O or NR 5 and R 5 signifies hydrogen or cyano, preferably of formulas IV and V in the form of a salt, of a complex, in the form of a solid solution, in the form of an occlusion or intercalation compound, the occlusion compound preferably being a cyclic or acyclic compound, preferably a carboxylic acid amide or a sulfonic acid amide , urea or substituted ureas as well as heterocycles, especially 2, 4, 6-tria ino-1,3,5-triazine, acetoguanamine and benzoguanamine. 9. Process for obtaining aqueous preparations of pigments according to claim 1, characterized in that the individual components of the preparation are homogenized together with water in wet comminution devices. 10. Preparations, characterized in that they contain at least one condensation product b1) based on 4, '-dihydroxydi phenylsulfone, sulphonated di tolyl ethers and formaldehyde; 4,4'-dihydroxydiphenylsulphone, phenolsulfonic acid and formaldehyde; 4, 4 '-dihydroxydiphenylsulphone, sodium bisulfite, formaldehyde and urea; Naphthalenesulfonic acid, 4,4'-dihydroxydiphenylsulphone and formaldehyde; sulfonated terphenyl and formaldehyde; or sulfonated 2-hydroxydiphenyl and formaldehyde, which have an inorganic salt content of less than 10% by weight, based on the preparation. 11. Preparations according to claim 9, characterized in that the condensation product b1) has a residual monomer content of less than 30% by weight, preferably less than 20% by weight, especially less than 10% by weight, based on to the condensation product bl). 12. Preparations according to claim 9, characterized in that the condensation product bl) has an average degree of condensation of 1 to 150, preferably 1 to 20, especially 1 to 5. 13. Use of the preparations according to the claim 9, such as tanning agents, blenders, auxiliary drilling agents or dispersing agents. 14. Use of the aqueous preparations of pigments according to claim 1, for the pigmenting of natural or synthetic materials. 15. Use of the aqueous pigment preparations according to claim 1, for the inking of bulk paper, of non-woven articles, sheets as well as paints for brush application on paper. 16. Use of the aqueous preparations of pigments according to claim 1, for the pigmenting of aqueous coating systems, especially polyacrylate, polyester or polyurethane systems, as well as for the inking of paints applied with a dispersion brush and for the manufacture of aqueous printing inks. 17. Use of the aqueous preparations of pigments according to claim 1, for pigmenting for ink jet printing.