DE102006051803A1 - Solid, formaldehyde-free pigment preparations - Google Patents

Abstract

The invention relates to solid, virtually formaldehyde-free pigment preparations consisting of at least one pigment and a resin, their preparation processes and their use in paints, lacquers, adhesives, inks or printing inks.

Description

The The invention relates to solid, virtually formaldehyde-free pigment preparations consisting of at least one pigment and a resin, their production process and their use in paints, varnishes, adhesives, inks or Printing inks.

used become these solid pigment preparations in coating materials such as paints, varnishes, adhesives, Inks or inks for the coating of objects from z. As metals and plastics. These coating compositions are suitable for all usual Application methods used in modern metal and plastic coating and the printing ink industry are used, such. B. the Spray application, the electrostatic spray application as well printing by various printing methods.

Usually Colored coating materials are prepared such that a first liquid pigment preparation is prepared, which is then painted with a parent lacquer.

at the production of pigment preparations become fillers and pigments in liquid Media dispersed. For this purpose, it is generally used dispersants, so for the effective dispersion of the solids required to reduce mechanical shear forces and at the same time as possible high fill levels too realize. The dispersants help break up agglomerates, wet and / or occupy the surface active compounds as the surface the particles to be dispersed and stabilize them against a undesirable Reagglomeration.

Network- and dispersants facilitate in the manufacture of colors and paints the incorporation of pigments and fillers, which are considered important Formulating ingredients the visual appearance and the physicochemical Significantly determine the properties of coatings. For an optimal Need to exploit these solids are evenly distributed in paints and varnishes second, once the distribution has been reached, it must stabilize become. The stabilizing component will in many cases too perceived by binder components. Such binders are also therefore valuable components for coating materials, because to faster drying and to increase the hardness of the resulting films contribute.

For solvent-based Coating materials are usually solventborne Pigment preparation on Basis made of various wetting and dispersing agents, the with different solventborne basecoats be painted. For aqueous Coating materials are usually also aqueous pigment preparation manufactured on the basis of various wetting and dispersing agents, those with different aqueous Stammlacken be painted.

In order to avoid the high costs arising from the production and storage of many pigment preparations, pigment preparations with universal compatibility with binders and solubility in organic solvents have also been developed. Such pigment preparations based on ketone-aldehyde resins are z. B. in the DE 44 04 809 described. The EP 1 078 946 describes the use of block copolymer polyalkylene oxides as dispersants for universal pigment preparations, which can be adjusted both aqueous and solvent-containing. The in the OZ 6490 ( DE 10 2005 012 316 ) described universal pigment preparations based on the combination of block copolymers, styrene oxide-containing polyalkylene oxides and ketone-aldehyde resins also have a broad compatibility with binders used and solubility in organic solvents used and in water. In addition, foaming in aqueous pigment preparations is suppressed.

In addition to water, organic solvents, and dispersants, all of these liquid pigment preparations generally contain other auxiliaries, such as anti-drying agents, rheology additives, anti-skinning agents, biocides, or agents for increasing the freeze-resistance. In order to avoid these aids and the handling of the energy and time-intensive dispersion of pigments, solid pigment preparations have been developed which can be dissolved in water or in organic solvents by simple stirring. The EP 0 702 055 describes the dispersing of pigments in high molecular weight organic binders, so-called stir-in pigments, for the preparation of colored, solvent-borne coatings. However, these pigments are not stabilized against reagglomeration, so that disturbances such as by specks are not reliably avoided.

The in the EP 0 702 062 described pigment preparations are conditioned. However, that will be used to improve the texture of the pigments inorganic salts of rosin resins, which remain on the one hand in the pigment preparation and can lead to disturbances in the organic coating. On the other hand, the dispersion is not optimal, so that when using phthalocyanine pigments must be ground several times wet.

In the EP 0 902 061 Vinyl pyrrolidone homopolymers or copolymers for preparing stir-in pigment preparations are described. These pigment preparations are particularly suitable for coloring aqueous industrial coatings or solvent-free plastics.

The DE 102 56 416 describes solid pigment preparations consisting of an organic pigment, a functionalized pigment derivative and a water-soluble surfactant additive selected from the group consisting of nonionic polyethers or, more particularly, derivatives thereof. However, these additives differ from those used in the pigment preparations of the present invention.

The US 6734231 describes a process for preparing a pigment composition by mixing a pigment and a urea-aldehyde resin or urea-ketone resin and then extruding. These resins are not free of formaldehyde.

The EP 0 432 480 describes masterbatches from mixtures of three essential components: a) acrylate resins, ketone resins or aldehyde resins, b) citric acid esters, acetyl citric acid esters or tartaric acid esters and c) dyes and / or pigments and additives. However, the use of citric acid ester, acetyl citric acid ester or tartaric acid ester leads to problems in the grinding of the pigments. In addition, the ketone resins or aldehyde resins contain formaldehyde.

The WO 2004/078852 describes a pigment preparation in which finely divided organic pigment particles are combined with inorganic pigment particles and these particles additionally have an organic macromolecular coating.

Of the The present invention was based on the object solid pigment preparations find that are free of formaldehyde, their composition preferably is easy and by a particularly easy dispersibility in application media of various kinds, especially by simple stir in (stir-in) in liquid Application media are distributable. By using this solid, formaldehyde-free pigment preparations in solvent-containing or solvent-free Applications should be given a high color strength and flocculation stability be.

The The object underlying the invention was able to surprisingly by the Use of at least one of the resins B) in combination with at least a pigment dissolved become.

Surprisingly It has been found that such solid, formaldehyde-free pigment preparations effortlessly in solventborne or solvent-free Coatings can be incorporated. They dissolve easily in an organic solvent or in a binder melt. The compatibility with many binders is given. The coatings obtained have a very good Course on.

• A) 40 bis 99 Gew.-% mindestens eines Pigmentes,
• B) 1 bis 60 Gew.-% mindestens eines carbonylhydrierten Ketonharzes und/oder eines carbonylhydrierten Keton/Aldehyd-Harzes und/oder eines carbonylhydrierten und kernhydrierten Keton/Aldehyd-Harzes auf der Basis von aromatischen Ketonen oder deren Umsetzungsprodukte mit mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- und/oder oder Polyisocyanat,
• C) 0 bis 50 Gew.-% mindestens eines anorganischen Füllstoffes

wobei die Summe der Gewichtsangaben der Komponenten A), B) und C) 100 Gew.-% beträgt.The invention relates to solid, formaldehyde-free pigment preparations, essentially containing

• A) 40 to 99% by weight of at least one pigment,
• B) 1 to 60 wt .-% of at least one carbonyl-hydrogenated ketone resin and / or a carbonyl-hydrogenated ketone / aldehyde resin and / or a carbonyl-hydrogenated and ring-hydrogenated ketone / aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate,
• C) 0 to 50 wt .-% of at least one inorganic filler

wherein the sum of the weights of components A), B) and C) is 100 wt .-%.

When Component A) can organic or inorganic pigments and carbon blacks are used.

Suitable organic pigments are, for example, azo pigments, azomethine pigments, metal complex pigments, anthraquinoid pigments, phthalocyanine pigments, polycyclic pigments, in particular those of thioindigo, quinacridone, dioxazine, pyrrolo, naphthalenetetracarboxylic, perylene, indanthrone, isoamidoline ( on), isoindolinone, flavanthrone, pyranthrone or isoviolanthrone series. mixtures or solid solutions of such pigments are also possible. Especially suitable are pigments from the group of the azo, dioxazine, pyrrolo (especially the diketopyrrolopyrrole pigments), quinacridone, phthalocyanine, indanthrone or isoindolinone pigments. Important organic pigments are those described in the Color Index. These include, for example, the group of CI Pigment Red 202, CI Pigment Red 122, CI Pigment Red 144, CI Pigment Red 170, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Brown 23, CI Pigment Yellow 13, CI Pigment Yellow 74, CI Pigment Yellow 83, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 147, CI Pigment Yellow 191.1, CI Pigment Orange 48, CI Pigment Orange 49, CI Pigment Orange 61, CI Pigment Orange 71, CI Pigment Blue 15, CI Pigment Blue 60, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 37, CI Pigment Green 7, CI Pigment Green 36.

suitable inorganic pigments are, for example, metal oxides, mixed Metal oxides, antimony yellow, lead chromates, lead chromosulfates, lead molybdate, Ultramarine blue, cobalt blue, manganese blue, chrome oxide green, hydrated chromium oxide green, Cobalt green, Metal sulfides, cadmium sulfoselenides, zinc ferrites or bismuth vanadates, alone or in mixtures.

When Carbon blacks can be gas soot, flame black or furnace blacks, used alone or in mixtures. These carbon blacks can be additionally oxidized and / or be bubbly.

It can also any mixtures of organic, inorganic pigments or Russians be used.

In principle, all carbonyl-hydrogenated ketone resins, carbonyl-hydrogenated ketone / aldehyde resins, carbonyl-hydrogenated and ring-hydrogenated ketone / aldehyde resins based on aromatic ketones are suitable. According to the content of harmful formaldehyde in the resins B) is greatly reduced. Formaldehyde-free means that the carbonyl-hydrogenated ketone-aldehyde resins according to the invention have a free formaldehyde content of less than 3 ppm, preferably less than 2.5 ppm, more preferably less than 2.0 ppm. Such resins B) are known, for example from DE 102006026758.3 . DE 102006026760.5 . DE 102006009079.9 . DE 102006009080.2 and are preferably used in the context of this invention. Also suitable are their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic di- or polyisocyanate as component B) in the solid pigment preparations.

When Ketones for the preparation of the carbonyl-hydrogenated ketone resins and the carbonyl-hydrogenated ketone / aldehyde resins are all ketones, especially acetone, acetophenone, methyl ethyl ketone, tert-butyl methyl ketone, Heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, Mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone and cyclooctanone, cyclohexanone and all alkyl-substituted cyclohexanones with one or more alkyl radicals having a total of 1 to 8 hydrocarbon atoms have, individually or in mixture. As examples alkyl-substituted Cyclohexanone can 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

in the Generally can but all in the literature for Ketone resin and ketone / aldehyde resin syntheses as suitably mentioned ketones, generally all C-H-acidic ketones used become. Preference is given to carbonyl-hydrogenated ketone and ketone / aldehyde resins based on the ketones acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone and heptanone alone or in admixture.

When Aldehyde component of the carbonyl-hydrogenated ketone / aldehyde resins are suitable in principle unbranched or branched aldehydes, such as. B. Formaldehyde, acetaldehyde, n-butyraldehyde, isobutyraldehyde, valeric aldehyde as well as dodecanal. In general, all in the literature for ketone-aldehyde resin syntheses be used as suitable called aldehydes. It is preferred however, formaldehyde is used alone or in mixtures.

The needed Formaldehyde is usually as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other uses of formaldehyde such. B. also the use para-formaldehyde or trioxane are also possible. aromatic Aldehydes, such as. As benzaldehyde, may in mixture with formaldehyde Also included.

Carbonyl-hydrogenated resins of acetophenone, cyclohexanone, 4-tert.-butylhexanone, 3,3,5-trimethylcyclohexanone and also heptanone alone or in mixture and formaldehyde are particularly preferably used as starting compounds for component B). To a lesser extent, non-hydrogenated Ke clay / aldehyde resins are used, but then have lower light fastness.

The resins of ketone and aldehyde are hydrogenated in the presence of a catalyst with hydrogen at pressures of up to 300 bar. The carbonyl group of the ketone-aldehyde resin is converted into a secondary hydroxy group. Depending on the reaction conditions, a part of the hydroxy groups can be split off, so that methylene groups result. To illustrate, the following scheme is used:

When Ketones for the preparation of the carbonyl-hydrogenated and ring-hydrogenated Ketone-aldehyde resins (component B) are all ketones that in addition to C-H-acidic protons have aromatic groups, in particular Arylalkylketones such. As methyl naphthyl ketone, acetophenone and / or its derivatives such. B. nuclear substituted acetophenone derivatives, such as hydroxy, methyl, ethyl, tert-butyl-cyclohexyl-acetophenone.

By the choice of the hydrogenation conditions of component B) and the hydroxy groups can be hydrogenated, so that cycloaliphatic rings formed. The ring-hydrogenated resins have OH numbers of 50 to 450 mg KOH / g, preferably, 100 to 350 mg KOH / g, more preferably from 150 to 300 mg KOH / g. The proportion of aromatic groups is below 50 wt .-%, preferably below 30 wt .-%, more preferably below 10 wt .-%. One method is in DE 33 34 631 described.

The Formaldehyde still present in the ketone resins and ketone / aldehyde resins is hydrogenated by this hydrogenation process to methanol, which from the Product is removed. Thus, the carbonyl-hydrogenated ketone / aldehyde resins practically free of formaldehyde.

The conversion of the carbonyl groups into secondary alcohols by hydrogenation of ketone-aldehyde resins has been practiced for a long time (e.g. DE 870 022 . DE 32 41 735 . JP 11012338 ). A typical and well-known product is synthetic resin SK from Degussa AG. The use of carbonyl- and ring-hydrogenated ketone / aldehyde resins based on ketones containing aromatic groups is also possible. Such a resin is in DE 33 34 631 described. The OH number of such products is very high at over 200 mg KOH / g.

Examples of suitable aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanates for preparing secondary products of hydrogenated ketone resins, carbonyl-hydrogenated ketone / aldehyde resins or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins are diisocyanates or polyisocyanates, cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, Phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, tolylene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, hexane diisocyanate such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate such as 1,6- Diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2,2,4-trimethylhexane (TMDI), nonanetriisocyanate such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecandibed and triisocyanate, dodecandi- and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl) methane (H ₁₂ MDI), isocyanatomethylcyclohexylisocyanate, 2,5 (2,6) -bis (isocyanato-methyl) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanato) cyclohexane (1, 3-H ₆ -XDI) or 1,4-bis (isocyanatomethyl) cyclohexane (1,4-H ₆ -XDI), alone or in admixture.

Another preferred class of polyisocyanates for the preparation of secondary products of the hydrogenated ketone resins, carbonyl-hydrogenated ketone / aldehyde resins or carbonyl-hydrogenated and ring-hydrogenated ketone / aldehyde resins are the compounds prepared by dimerization, trimerization, allophanatization, biuretization and / or urethanization of the simple diisocyanates with more as two isocyanate groups per molecule, for example the Usmetzungsprodukte these simple diisocyanates, such as. IPDI, TMDI, HDI and / or H ₁₂ MDI with polyhydric alcohols (eg glycerol, trimethylolpropane, pentaerythritol) or polyvalent polyamines, or the triisocyanurates obtained by trimerization of the simple diisocyanates, such as IPDI, HDI and H ₁₂ MDI, are available.

It is also possible to use part of the carbonyl-hydrogenated ketone resins, carbonyl-hydrogenated ketone / alde hyd resins or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins by further hydroxy-functional polymers such. As hydroxy-functional polyesters and / or polyacrylates to replace. As a result, properties such. B. flexibility or hardness can be set more targeted (claim 2).

to Accelerating the reaction can be a suitable catalyst for Preparation of the resins from hydrogenated ketone resins and / or a carbonyl-hydrogenated ketone / aldehyde resins and / or a carbonyl-hydrogenated and nuclear-hydrogenated ketone-aldehyde resins based on aromatic Ketones and at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate are used. From an economic point of view this is necessary. in principle For example, all tin-free compounds that have an OH-NCO reaction are suitable accelerate.

organotin compounds, such as dibutyltin dilaurate (DBTL) or dibutyltin diactate (DBTA) known good Catalysts. Catalysts based on the metals bismuth, zirconium, Iron or aluminum are also well suited, such as. B. Carboxylates, Chelates and complexes.

The same applies to purely organic catalysts such. B. tert. Amines for example 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), N, N-dimethylcyclohexylamine (DMCA) or 1,5-diazabicyclo [2.3.0] non-5-ene (DBN).

Of the Melting range of the reaction products prepared from hydrogenated Ketone resins and / or a carbonyl-hydrogenated ketone / aldehyde resins and / or a carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resins based on aromatic ketones and at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate is above 140 ° C, preferably above 145 ° C, more preferably above 150 ° C.

such Products have been known for a long time. A typical product is synthetic resin 1201 of Degussa AG.

When Component C) can also fillers be used. They are usually powdery, in the application medium practically insoluble Substances. They become predominant of course occurring minerals by mining, cleaning, grinding and subsequent classification won in grain fractions. But also synthetic products, such as Sulfates or carbonates, are used as fillers when it for example, purity (brightness) or special fineness goes. In contrast to pigments, fall substances i. d. R. a low hiding power. In addition to the enlargement of the Volume (cheapening) they show very special effects in the film, such as B. reflection, surface structure, Abrasion or stone chip resistance. Their use is determined by their particle size, particle size distribution, Particle shape, particle structure, hardness, density, color, wettability, abrasiveness, surface adsorption, Refractive index, chemical composition, purity, resistance and price predetermined.

suitable fillers for use in the solid pigment preparations of the invention are, for example, those based on kaolin, talc, mica, other silicates, quartz, Christobalite, wollastonite, perlite, diatomaceous earth, Fiber fillers Aluminum hydroxide, barium sulfate or calcium carbonate.

• A) 40 bis 99 Gew.-% mindestens eines Pigmentes,
• B) 1 bis 60 Gew.-% mindestens eines carbonylhydrierten Ketonharzes und/oder eines carbonylhydrierten Keton/Aldehyd-Harzes und/oder eines carbonylhydrierten und kernhydrierten Keton-Aldehyd-Harzes auf der Basis von aromatischen Ketonen oder deren Umsetzungsprodukte mit mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- und/oder oder Polyisocyanat,
• C) 0 bis 50 Gew.-% mindestens eines anorganischen Füllstoffes

wobei die Summe der Gewichtsangaben der Komponenten A), B) und C B) 100 Gew.-% beträgt,
dadurch gekennzeichnet,
dass eine Suspension aus dem Pigment A), carbonylhydrierten Ketonharz und/oder carbonylhydrierten Keton/Aldehyd-Harz und/oder carbonylhydrierten und kernhydrierten Keton-Aldehyd-Harz auf der Basis von aromatischen Ketonen oder deren Umsetzungsprodukte mit mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- und/oder oder Polyisocyanat B) und ggf. dem anorganischen Füllstoff C) in einem organischen Lösemittel und/oder Wasser hergestellt wird, die Suspension in einem geeigneten Aggregat dispergiert und die feste Pigmentpräparation isoliert wird.The invention also provides a process for the preparation of solid, formaldehyde-free pigment preparations, essentially containing

• A) 40 to 99% by weight of at least one pigment,
• B) 1 to 60 wt .-% of at least one carbonyl-hydrogenated ketone resin and / or a carbonyl-hydrogenated ketone / aldehyde resin and / or a carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate,
• C) 0 to 50 wt .-% of at least one inorganic filler

the sum of the weights of components A), B) and CB) being 100% by weight,
characterized,
that a suspension of the pigment A), carbonyl-hydrogenated ketone resin and / or carbonyl-hydrogenated ketone / aldehyde resin and / or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic Di- and / or polyisocyanate B) and optionally the inorganic filler C) is prepared in an organic solvent and / or water, the suspension is dispersed in a suitable aggregate and the solid pigment preparation is isolated.

When Dispersing units come in particular with ball mills, agitator ball mills horizontal or vertical arrangement or radial agitator mills in Consideration. For example, it can also be a Dispermat, a Scandex mixer, a Red Devil, a single-roller chair, a three-roll chair or a Used bead mill become. The isolation of the solid pigment preparation can be done with the usual Drying facilities take place, for example in a fluidized bed, a spray dryer, a belt dryer or a vacuum dryer. The deagglomeration in the context of the preparation of the pigment preparation of the invention therein contained agglomerates, for example by means of hammer mills, pin mills, impact mills or classifier, but can also already be integrated into the drying process, z. B. in the form of a Mahltrocknung.

The solid, formaldehyde-free pigment preparations can in all known to those skilled solvent-containing as solvent-free Coating systems such as paints, inks, adhesives, inks or Printing inks are introduced. These systems can be physical, for example drying, oxidatively drying or otherwise reactive in 1K or Be 2K paints.

It There are a variety of physically drying resins, for example Nitrocellulose, polyvinyl butyral, VC copolymers, acrylates, methacrylates, Cellulose esters, cellulose ethers, hydrocarbon resins, phenolic resins, Rosin resins, maleate resins, polystyrene resins, silicone resins, Rubber-based coating resins such as cyclo rubber, chlorinated rubber, chlorinated polyolefins or oligobutadienes, polyolefins, polyvinyl esters, polyvinyl alcohols, Polyvinyl acetals, epoxies, amino resins, amido resins and polyester resins. Oxidatively drying coating materials are, for example, alkyd resins. 1K coating materials are based, for example, on (meth) acrylate, Epoxy, polyvinyl acetate, polyester or polyurethane resins. These Resins can also unsaturated be, d. H. Acrylate or methacrylate double bonds contain as for example (meth) acrylated (meth) acrylate resins, epoxy (meth) acrylate resins, Polyester (meth) acrylate resins, polyether (meth) acrylate resins or polyurethane (meth) acrylate resins. 1K coating materials are also those based on hydroxyl groups Polyacrylate or polyester resins with melamine resins or blocked Polyisocyanate resins as crosslinkers. 2K coating materials are for example those based on Polyepoxidsystemen or of hydroxyl-containing Polyacrylate or polyester resins with unblocked polyisocyanate resins as a crosslinker.

In the coating systems can all adjuvants and additives known to those skilled in the art are used. These include for example defoamers, Ventilator, Rheology aids, surface additives, the z. B. lubricity, Scratch resistance, anti-blocking, course and shine influence, Substrate wetting additives, driers, stabilizers or biocides.

• A) 40 bis 99 Gew.-% mindestens eines Pigmentes,
• B) 1 bis 60 Gew.-% mindestens eines carbonylhydrierten Ketonharzes und/oder eines carbonylhydrierten Keton/Aldehyd-Harzes und/oder eines carbonylhydrierten und kernhydrierten Keton-Aldehyd-Harzes auf der Basis von aromatischen Ketonen oder deren Umsetzungsprodukte mit mindestens einem aromatischen, aliphatischen und/oder cycloaliphatischen Di- und/oder oder Polyisocyanat,
• C) 0 bis 50 Gew.-% mindestens eines anorganischen Füllstoffes

wobei die Summe der Gewichtsangaben der Komponenten A), B) und C) 100 Gew.-% beträgt,
in Farben, Lacken, Klebstoffen, Tinten oder Druckfarben.The invention therefore also relates to the use of solid, formaldehyde-free pigment preparations, essentially containing

• A) 40 to 99% by weight of at least one pigment,
• B) 1 to 60 wt .-% of at least one carbonyl-hydrogenated ketone resin and / or a carbonyl-hydrogenated ketone / aldehyde resin and / or a carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate,
• C) 0 to 50 wt .-% of at least one inorganic filler

the sum of the weights of components A), B) and C) being 100% by weight,
in paints, varnishes, adhesives, inks or inks.

The solid, formaldehyde-free pigment preparations are characterized by a particularly easy dispersibility in Application media of various kinds, especially by simple stir in (stir-in) in liquid Application media, off. By using these solid pigment preparations in solvent-based or solvent-free Applications such as powder coatings become coating systems obtained having a high tinting strength, a high gloss lind have a good Flockulationsstabilität.

The The following examples are intended to further illustrate the invention, but do not restrict their scope:

Examples

1) Preparation of a carbonyl-hydrogenated Ketone / aldehyde resin (not according to the invention)

1200 g acetophenone, 220 g methanol, 0.3 g benzyltributylammonium chloride and 360 g of a 30% aqueous formaldehyde solution were submitted and placed under tubes homogenized. Then, with stirring, the addition of 32 g of a 25% aqueous Sodium hydroxide solution. At 80 to 85 ° C followed by stirring the addition of 655 g of a 30% aqueous formaldehyde solution over 90 minutes. The stirrer was stirring after 5 h at reflux temperature turned off and the watery Phase separated from the resin phase. The crude product was acidified with acetic acid Washed water until a melt sample of the resin appears clear. Then The resin was dried by distillation.

It 1270 g of a slightly yellowish resin were obtained. The resin was clear and brittle and owned one Melting point of 72 ° C. It was z. B. in acetates such. As butyl and ethyl acetate, in aromatics such as toluene and xylene soluble. It was insoluble in ethanol.

400 g of the resin thus prepared were dissolved in 650 g of tetrahydrofuran (water content about 7%) solved. Then, the hydrogenation was carried out at 260 bar and 160 ° C in one Autoclave (Parr) with catalyst basket containing 100 mL of a commercial Ru catalyst (3% Ru on alumina) was fallen. After 20 h the reaction mixture was over a filter is drained from the reactor.

Properties: Hydroxyl number 315 mg KOH / g; Melting point 116 ° C; Color number according to Gardner (50% in ethyl acetate) 0.2.

The hydrogenated resin was in ethanol, dichloromethane, ethyl acetate, butyl acetate, Isopropanol, acetone and diethyl ether soluble. It was insoluble in nonpolar solvents like n-hexane or white spirit.

2) Preparation of the solid according to the invention pigment preparation

380 g Spezialschwarz 4 (C.I. Pigment Black 7 from Degussa AG) with 520 g of water to an aqueous Pressed cake stirred. In a separate container 467 g of the carbonyl-hydrogenated ketone / aldehyde resin 1) in 467 g of ethanol dissolved and 76.5 g ULTRA Talc 609 (from Barretts Minerals Inc.). The Talc / resin mixture was added to the pigment presscake and dispersed in a dissolver. The pigment dispersion was in a Drying oven dried and micropulverized.

3) Preparation of a solvent-containing pigment preparation (not according to the invention)

280 g of special black 4 were mixed with 520 g of a 50% solution of carbonyl-hydrogenated ketone / aldehyde resin 1) in methoxypropylacetates and 187 g Disperbyk 163 (from Byk-Chemie) mixed and 1 mm glass beads in the volume ratio 1: 1 added. The Mixture was dispersed in Dispermat CV for 80 minutes at 3000 rpm.

4) Preparation of the solventborne basecoat (not according to the invention)

The starting materials listed in the table were stirred with the aid of 2 mm glass beads in the Dispermat CV for 20 minutes at 2400 rpm and a jacket temperature of 25 ° C. Subsequently, the white Mittelölalkydlack was dried for 24 h at room temperature. The ratio of binder (solid) to white pigment was 1: 0.8. Table 1: Composition of the parent lacquer feedstocks Amount (wt%) Alkydal F 49 (55%) 61.92 Kronos 2310 27.24 Ca siccative (5% Ca) 0.77 Co-siccative (10% Co) 0.53 Zr siccative (12% Zr) 0.18 Mn-siccative (10% Mn) 0.10 Octa-Soligen VP 033 0.26 xylene 4.5 methoxypropylacetate 2.1 white spirit 2.1 Borchinox M2 0.3 total 100.0

5) Preparation of the coating compositions of the invention

For the preparation of coating materials, the pigment preparations 2) and 3) were initially charged and the white stock paint (4) was added in portions with stirring. Table 2 gives the coating compositions and their properties. Table 2: Coating Compositions formulation example comparison White paint from 4) 150.0 g 150.0 g Black, solid pigment preparation from 2) 3.2 g - Black pigment preparation from 3) - 4.2 g butylglycol 3.0 g 3.0 g Hydropalat 535 N 2.3 g 2.3 g % Black pigment on white pigment 3.2 3.2 Technical properties of the coatings on normal steel Layer thickness (μm) 23 23 Pendulum hardness after king after 28 d 85 84 Cross-hatching after 28 d 0 0 Erichsen cupping (mm) after 28 d 6.5 6.5 Gloss 20 ° / 60 ° after 28 d 75/87 74/87 Glossy haze after 28 d 50-53 51-55 ΔE rub out 0.96 0.99

The exemplified coating composition based on the Solid, formaldehyde-free invention pigment preparation and a solvent-containing, white Alkyd paint had one high gloss and good mechanical and coloristic properties. These properties were with a coating composition based on a solvent-containing pigment preparation comparable.

Claims (26)

Solid, formaldehyde-free pigment preparations, essentially containing A) 40 to 99 wt .-% of at least one pigment, B) 1 to 60 wt .-% of at least one carbonyl-hydrogenated ketone resin and / or a carbonyl-hydrogenated Ke clay / aldehyde resin and / or a carbonyl-hydrogenated and ring-hydrogenated ketone / aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate, C) 0 to 50 wt .-% of at least one inorganic filler wherein the sum of the weights of components A), B) and C) is 100 wt .-%. Solid, formaldehyde-free pigment preparations, essentially containing A) 40 to 99% by weight of at least one pigment, B) 1 to 60 wt .-% of at least one carbonyl-hydrogenated ketone resin and / or a carbonyl-hydrogenated ketone / aldehyde resin and / or a carbonyl-hydrogenated and ring-hydrogenated ketone / aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic Di- and / or polyisocyanate, with at least one additional use another hydroxy-functionalized polymer, C) 0 to 50 wt .-% of at least one inorganic filler where the sum the weights of components A), B) and C) is 100 wt .-%. Solid, formaldehyde-free pigment preparations at least one the previous claims, characterized in that as component A) organic or inorganic Pigments or carbon blacks used alone or in mixtures. Solid, formaldehyde-free pigment preparations after at least one of the previous characterized, the organic pigments selected from azo pigments, azomethine pigments, metal complex pigments, anthraquinoid Pigments, phthalocyanine pigments, polycyclic pigments of thioindigo, Quinacridone, dioxazine, pyrrolo, naphthalenetetracarboxylic, perylene, Indanthrone, isoamidoline (on), isoindolinone, flavanthrone, pyranthrone or isoviolanthrone series alone or in mixtures. Solid, formaldehyde-free pigment preparations after at least one of the preceding claims, characterized in that inorganic pigments are selected from Metal oxides, mixed metal oxides, antimony yellow, lead chromates, lead chromosulfates, Lead molybdate, ultramarine blue, cobalt blue, manganese blue, chrome oxide green, hydrated chromium oxide green, Cobalt green, Metalsulfide, cadmium sulfoselenide, zinc ferrites or bismuth vanadates used alone or in mixtures. Solid, formaldehyde-free pigment preparations after at least one of the preceding claims, characterized in that used as carbon blacks gas blacks, Flammruße or Furnaceruße become. Solid, formaldehyde-free pigment preparations after at least one of the preceding claims, characterized in that for the preparation of component B) C-H-acid Ketones are used. Solid, formaldehyde-free pigment preparations after at least one of the preceding claims, characterized in that in the carbonyl-hydrogenated ketone and Ketone / aldehyde resins of component B) ketones selected from Acetone, acetophenone, methyl ethyl ketone, tert-butyl methyl ketone, heptanone-2, Pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclododecanone, Mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, cycloheptanone, Cyclooctanone, cyclohexanone, alkyl-substituted cyclohexanones with one or more alkyl radicals having a total of 1 to 8 hydrocarbon atoms have, used as starting compounds alone or in mixtures become. Solid, formaldehyde-free pigment preparations after the previous one Claim, characterized in that in the carbonyl-hydrogenated Ketone and ketone / aldehyde resins of component B) 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone or 3,3,5-trimethylcyclohexanone used become. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that in the carbonyl-hydrogenated ketone and ketone / aldehyde resins, Acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone or heptanone alone or in mixtures. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that as the aldehyde component of the carbonyl-hydrogenated ketone-aldehyde resins and carbonyl- and ring-hydrogenated ketone / aldehyde resins in component B) formaldehyde, acetaldehyde, n-butyraldehyde and / or isobutyraldehyde, Valerianaldehyde, dodecanal, used alone or in mixtures become. Solid, formaldehyde-free pigment preparations according to the previous claim, characterized in that formaldehyde and / or para-formaldehyde and / or trioxane. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that carbonyl hydrogenation products of the resins of acetophenone, 4-tert-butyl methyl ketone, Cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5-trimethylcyclohexanone, Heptanone, alone or in mixture, and formaldehyde as a component B) are used. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that in the carbonyl- and ring-hydrogenated ketone / aldehyde resins of Component B) aryl-alkyl ketones can be used. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that in the carbonyl- and ring-hydrogenated ketone-aldehyde resins Component A), ketones selected acetophenone, nucleus-substituted acetophenone derivatives, such as hydroxy, Methyl, ethyl, tert-butyl, cyclohexyl-acetophenone, methylnaphthyl ketone are included. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized in that diisocyanates as component B) selected from cyclohexane diisocyanate, methylcyclohexane diisocyanate, ethylcyclohexane diisocyanate, phenylene diisocyanate, propylcyclohexane diisocyanate, methyldiethylcyclohexane diisocyanate, toluene diisocyanate, bis (isocyanatophenyl) methane, propane diisocyanate, butane diisocyanate, pentane diisocyanate, Hexane diisocyanate, such as hexamethylene diisocyanate (HDI) or 1,5-diisocyanato-2-methylpentane (MPDI), heptane diisocyanate, octane diisocyanate, nonane diisocyanate, such as 1,6-diisocyanato-2,4,4-trimethylhexane or 1,6-diisocyanato-2, 2,4-trimethylhexane (TMDI), nonane triisocyanate, such as 4-isocyanatomethyl-1,8-octane diisocyanate (TIN), decane and triisocyanate, undecanediisocyanate and triisocyanate, dodecanedi and triisocyanates, isophorone diisocyanate (IPDI), bis (isocyanatomethylcyclohexyl ) methane (H ₁₂ MDI), isocyanatomethylmethylcyclohexylisocyanate, 2,5 (2,6) -bis (isocyanato-methyl ) bicyclo [2.2.1] heptane (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (1,3-H ₆ -XDI) or 1,4-bis (isocyanato-methyl) cyclohexane (1,4-H ₆ -XDI), alone or in mixtures. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that polyisocyanates prepared by dimerization, trimerization, Allophanatization, biuretization and / or urethanization easier Diisocyanates, used as component B). Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized in that are used as component B) isocyanates based on IPDI, TMDI, H ₁₂ MDI and / or HDI. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized in that the melting range of the reaction product of hydrogenated ketone resins and / or a carbonyl-hydrogenated ketone / aldehyde resins and / or a carbonyl-hydrogenated and nuclear-hydrogenated ketone-aldehyde resins based on aromatic Ketones and at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate above 140 ° C, preferred above 145 ° C, particularly preferably above 150 ° C. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that hydroxy-functional polymers for the preparation of the component B) are used. Solid, formaldehyde-free pigment preparations according to at least one of the preceding claims, characterized that as component C) compounds based on kaolin, talc, Mica, other silicates, quartz, Christobalite, wollastonite, perlite, Diatomaceous earth, fiber fillers, Aluminum hydroxide, barium sulfate or calcium carbonate used become. A process for the preparation of solid, virtually formaldehyde-free pigment preparations, substantially containing A) 40 to 99 wt .-% of at least one pigment, B) 1 to 60 wt .-% of at least one carbonyl-hydrogenated ketone resin and / or a carbonyl-hydrogenated ketone / aldehyde resin and or a carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, alipha and / or cycloaliphatic di- and / or polyisocyanate, C) 0 to 50 wt .-% of at least one inorganic filler wherein the sum of the weights of components A), B) and C) is 100 wt .-%, characterized in that a suspension of the pigment A), carbonyl-hydrogenated ketone resin and / or carbonyl-hydrogenated ketone / aldehyde resin and / or carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic di- and / or polyisocyanate B) and optionally the inorganic filler C) is prepared in an organic solvent and / or water, the suspension is dispersed in a suitable aggregate and the solid pigment preparation is isolated. Method of making solid, practical formaldehyde-free pigment preparations according to claim 28, characterized in that the suspension in a ball mill, an agitating ball mill, a Radial agitator mill, one Dispermat, a Scandex mixer, a Red Devil, a single-roller chair, a three-roll mill or a bead mill is dispersed. Method of making solid, practical formaldehyde-free pigment preparations according to at least one of the claims 28 to 29, characterized in that the solid pigment preparation in a fluidized bed, a spray dryer, a belt dryer or a vacuum dryer is isolated. Method of making solid, practical formaldehyde-free pigment preparations according to at least one of the claims 28 to 30, characterized in that the solid pigment preparation after their isolation in hammer mills, Pin mills, impact mills or classifier mills is deagglomerated. Use of solid, virtually formaldehyde-free Pigment preparations, essentially containing A) 40 to 99 wt .-% of at least one pigment, B) I to 60 wt .-% of at least one carbonyl-hydrogenated Ketone resin and / or a carbonyl-hydrogenated ketone / aldehyde resin and / or a carbonyl-hydrogenated and ring-hydrogenated ketone-aldehyde resin based on aromatic ketones or their reaction products with at least one aromatic, aliphatic and / or cycloaliphatic Di- and / or polyisocyanate, C) 0 to 50 wt .-% at least an inorganic filler in which the sum of the weights of components A), B) and C) 100 Wt .-%, in Paints, varnishes, adhesives, inks or inks.