DE102006026761A1 - Universal pigment preparations - Google Patents

Abstract

The invention relates to solid or liquid universal pigment preparations consisting of at least one pigment and a resin, their preparation process and their use in paints, varnishes, adhesives, inks or printing inks.

Description

The The invention relates to universal pigment preparations consisting of at least a pigment and a resin, their production process and their Use in paints, varnishes, adhesives, inks or inks.

used become these 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 as well as the Ink industry can be used, such. B. the spray application, the electrostatic spray application and printing by means of different printing methods.

Usually become colored. Coating materials prepared such that initially a 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 preparations manufactured on the basis of various wetting and dispersing agents, 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 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 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. Furthermore, these pigment preparations are not suitable for aqueous coatings, that is not universal.

In the EP 902 061 Vinylpyrrolidone homopolymers or copolymers for the preparation of stir-in pigment preparations are described. These pigment preparations are particularly suitable for coloring aqueous industrial coatings or solvent-free plastics. They are not suitable for solvent-based coatings.

The US 6,734,231 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 pigment compositions are suitable only for solventborne and powder coating systems.

The EP 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. Furthermore, the masterbatches are not suitable for aqueous applications.

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. They can be used to color many materials. However, the additives used differ from those used in the pigment preparations of the invention.

The in the EP 702,062 described pigment preparations are universal. However, to improve the texture of the pigments, inorganic salts of rosin resins are used, which on the one hand remain 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.

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. They can be used both in solventborne aqueous coating systems and for coloring plastics. However, these additives differ from those used in the pigment preparations of the present invention.

Of the The present invention was based on the object pigment preparations to find the universal, d. H. in solvent-based, solvent-free or aqueous Applications that are usable and which by a particularly light Dispersibility in application media of various kinds, especially by simply stirring (stir-in) in liquid Application media are distributable. By using this liquid or solid 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 a composition of at least one block copolymer, styrene oxide-containing polyalkylene oxide and a ketone-aldehyde resin, optionally with the concomitant use of at least one solvent, dissolved in combination with at least one pigment.

Surprisingly it has been found that such liquid or solid pigment preparations effortlessly in solvent-containing, solvent-free or coatings can be incorporated. They dissolve easily in an organic Solvents in a binder melt or in water. The compatibility too many binders, polar and nonpolar, is given. The coatings obtained have a very good course and an excellent color strength on.

• A) 40 bis 99 Gew.-% mindestens eines Pigmentes,
• B) 1 bis 60 Gew.-% einer Zusammensetzung, im Wesentlichen enthaltend das Mischungsprodukt von
• i) 95 bis 5 Gew.-% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids, mit
• ii) 5 bis 95 Gew.-% eines nicht hydrierten Keton-Aldehyd-Harzes, und
• iii) 0 bis 80 Gew.-% mindestens eines Lösemittels, wobei die Summe der Gewichtsangaben von Komponente i) bis iii) 100 Gew.-% beträgt,
• C) 0 bis 50 Gew.-% mindestens eines anorganischen Füllstoffes,
• D) 1 bis 40% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids,

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

• A) 40 to 99% by weight of at least one pigment,
• B) 1 to 60% by weight of a composition substantially containing the product of the mixture of
• i) 95 to 5 wt .-% of at least one block copolymer, styrene oxide-containing polyalkylene oxide, with
• ii) from 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and
• iii) 0 to 80% by weight of at least one solvent, where the sum of the weights of component i) to iii) is 100% by weight,
• C) 0 to 50% by weight of at least one inorganic filler,
• D) 1 to 40% of at least one block copolymeric, styrene oxide-containing polyalkylene oxide,

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

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

In Organic pigments to be considered are, for example, azo pigments, Azomethine pigments, metal complex pigments, anthraquinoid pigments, Phthalocyanine pigments, polycyclic pigments, especially those 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. Particularly suitable are pigments from the group of the azo, dioxazine, Pyrrolo (especially the Diketopyrrolopyrrolpigmente), quinacridone Phthalocyanine, indanthrone or isoindolinone pigments. Important Organic pigments are those described in the Color Index become. This includes for example, the group of C.I. Pigment Red 202, C.I. Pigment Red 122, C.I. Pigment Red 144, C.I. Pigment Red 170, C.I. Pigment Red 177, C.I. Pigment Red 179, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment 264, C.I. Pigment Brown 23, C.I. Pigment Yellow 13, C.I. pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 109, C.I. pigment Yellow 110, C.I. Pigment Yellow 147, C.I. Pigment Yellow 191.1, C.I. pigment Orange 48, C.I. Pigment Orange 49, C.I. Pigment Orange 61, C.I. pigment Orange 71, C.I. Pigment Blue 15, C.I. Pigment Blue 60, C.I. pigment violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 37, C.I. Pigment Green 7, C.I. pigment Green 36th

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.

The compositions used as component B) contain as wetting agents and dispersant at least one block copolymer, styrene oxide-containing Polyalkylene oxide i) and at least one non-hydrogenated ketone-aldehyde resin ii). In principle, all block copolymers are styrene oxide-containing Polyalkylene oxides as component i) suitable.

The block copolymers preferably used in the invention, styrene oxide-containing polyalkylene oxides i) are z. B. in the EP 1 078 946 described. They have the general formula I: R ¹ O (SO) _a (EO) _b (PO) _c (BO) _d R ² I where R ¹ denotes a straight-chain or branched or cycloaliphatic radical having 8 to 13 carbon atoms,
R ² = hydrogen, an acrylic radical, alkyl radical or carboxylic acid radical having in each case 1 to 8 C atoms,
SO = stryene oxide,
EO = ethylene oxide,
PO = propylene oxide,
BO = butylene oxide and
a = 1 to 1.9,
b = 3 to 50,
c = 0 to 3,
d = 0 to 3
means
where a, c or d is other than 0, and b> = a + c + d.

in principle are all unhydrogenated ketone-aldehyde resins as component ii) suitable.

When Ketones for the preparation of component ii) can all known ketones be used. These are ketones with aliphatic, cycloaliphatic, aromatic hydrocarbon radicals, wherein these same or different and in turn with the said hydrocarbon radicals may be substituted in the hydrocarbon chain as well as optionally phenols and / or urea or its derivatives. For example, you can as ketones acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, Methyl isobutyl ketone, cyclohexanone, 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, 3,3,5-trimethylcyclohexanone, cyclopentanone, Mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, Cycloheptanone, cyclooctanone and cyclododecanone can be used.

The preferred non-hydrogenated ketone-aldehyde resins ii) used in the DE 44 04 809 are described, are prepared from cycloaliphatic ketones, aldehyde and optionally other monomers.

• I. 40 bis 100 Mol-%, bezogen auf alle eingesetzten Ketone, mindestens eines alkylsubstituierten Cyclohexanons mit einem oder mehreren Alkylresten mit 1 bis 8 Kohlenstoffatomen,
• II. 0,8 bis 2,0 mol mindestens eines aliphatischen Aldehyds, bezogen auf 1 mol aller eingesetzten Ketone und
• III. 0 bis 60 Mol-%, bezogen auf alle eingesetzten Ketone, weitere Ketone mit aliphatischen, cycloaliphatischen, aromatischen Kohlenwasserstoffresten, wobei diese gleich oder verschieden und wiederum mit den genannten Kohlenwasserstoffresten in der Kohlenwasserstoffkette substituiert sein können sowie gegebenenfalls Phenole und/oder Harnstoff oder seine Derivate, enthalten.

These contain unhydrogenated ketone-aldehyde resins

• I. 40 to 100 mol%, based on all ketones used, of at least one alkyl-substituted cyclohexanone having one or more alkyl radicals having 1 to 8 carbon atoms,
• II. 0.8 to 2.0 mol of at least one aliphatic aldehyde, based on 1 mol of all ketones used and
• III. 0 to 60 mol%, based on all ketones used, other ketones with aliphatic, cycloaliphatic, aromatic hydrocarbon radicals, which may be the same or different and in turn substituted with said hydrocarbon radicals in the hydrocarbon chain and optionally phenols and / or urea or its derivatives , contain.

When Examples of alkyl-substituted cyclohexanones I can be 4-tert-amylcyclohexanone, 2-sec-butyl cyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

Particularly preferred C ₁ - to C ₈ -alkyl-substituted cyclohexanones are 4-tert-butylcyclohexanone and 3,3,5-trimethylcyclohexanone.

When Aldehyde component in general and especially as II. Are suitable in principle unbranched or branched aldehydes, such as. B. formaldehyde, Acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and dodecanal, etc., however, formaldehyde is preferred alone or in mixtures. in the Generally can but all in the literature for Ketonharzsynthesen be used as suitable called aldehydes.

The preferred formaldehyde is usually as about 20 to 40 wt .-% aqueous or alcoholic solution (For example, in methanol or butanol) used. Other uses of formaldehyde such as. As well as the use as para-formaldehyde or trioxane are also possible. Aromatic aldehydes, such as. As benzaldehyde, in mixtures with formaldehyde Also included. Preference is given to an aqueous or alcoholic solution of Formaldehyde.

For the ketone component III. all ketones are especially acetone, acetophenone, methyl ethyl ketone, Heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, cyclohexanone, Cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanqone, Cycloheptanone and cyclooctanone. Preference is given to acetophenone and cyclohexanone.

The mixing ratio the invention used block copolymers, styrene oxide-containing polyalkylene oxides and the ketone-aldehyde resins is 95: 5 to 5:95. If you use more than one in this mixture For reasons of viscosity, 50% by weight of ketone-aldehyde resin must be an auxiliary solvent B) iii) are used.

When Component iii) is water or at least one organic solvent into consideration. Also mixtures are possible, provided the miscibility between water and organic solvent. To the organic solvents counting for example, alcohols, esters, ketones, ethers, glycol ethers, aromatic hydrocarbons, hydroaromatic hydrocarbons, halogenated hydrocarbons, Terpene hydrocarbons, aliphatic hydrocarbons, ester alcohols, Dimethylformamide or dimethyl sulfoxide.

As component C) also fillers can be used. They are usually powdery, practically insoluble in the application medium substances. They are mainly obtained from naturally occurring minerals by mining, cleaning, grinding and subsequent classification in grain fractions. But even synthetic products, such as sulfates or carbonates, are used as fillers, for example, when it comes to purity (brightness) or special fineness. In contrast to pigments, fillers generally have a low hiding power. In addition to the increase in volume (cheapening) they show in the film very special effects, such. As reflection, surface texture, abrasion or stone chip resistance. Their use is predetermined by their particle size, particle size distribution, particle shape, particle structure, hardness, density, color, wettability, abrasiveness, surface adsorption, refractive index, chemical composition, purity, durability and price.

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.

When Component D) are all block copolymers, styrene oxide-containing Polyalkylene oxides, as already described under B) i) are.

• A) 40 bis 99 Gew.-% mindestens eines Pigmentes,
• B) 1 bis 60 Gew.-% einer Zusammensetzung, im Wesentlichen enthaltend das Mischungsprodukt von
• i) 95 bis 5 Gew.-% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids, mit
• ii) 5 bis 95 Gew.-% eines nicht hydrierten Keton-Aldehyd-Harzes, und
• iii) 0 bis 80 Gew.-% mindestens eines Lösemittels, wobei die Summe der Gewichtsangaben von Komponente i) bis iii) 100 Gew.-% beträgt,
• C) 0 bis 50 Gew.-% mindestens eines anorganischen Füllstoffes,
• D) 1 bis 40% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids,

wobei die Summe der Gewichtsangaben der Komponenten A), B, C) und D) 100 Gew.-% beträgt,
dadurch gekennzeichnet, dass
eine Suspension aus dem Pigment A), der Zusammensetzung B) gegebenenfalls dem anorganischen Füllstoff C) und gegebenenfalls dem blockcopolymeren, styrenoxidhaltigen Polyalkylenoxid in einem organischen Lösemittel und/oder Wasser hergestellt wird, die Suspension in einem geeigneten Aggregat dispergiert und die Pigmentpräparation isoliert wird.The invention also provides a process for the preparation of universal pigment preparations, essentially containing

• A) 40 to 99% by weight of at least one pigment,
• B) 1 to 60% by weight of a composition substantially containing the product of the mixture of
• i) 95 to 5 wt .-% of at least one block copolymer, styrene oxide-containing polyalkylene oxide, with
• ii) from 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and
• iii) 0 to 80% by weight of at least one solvent, the sum of the weights of components i) to iii) being 100% by weight,
• C) 0 to 50% by weight of at least one inorganic filler,
• D) 1 to 40% of at least one block copolymeric, styrene oxide-containing polyalkylene oxide,

the sum of the weights of components A), B, C) and D) being 100% by weight,
characterized in that
a suspension of the pigment A), the composition B) optionally the inorganic filler C) and optionally the block copolymer, styrene-containing polyalkylene oxide is prepared in an organic solvent and / or water, the suspension is dispersed in a suitable aggregate and the pigment preparation is isolated.

• A) 40 bis 99 Gew.-% mindestens eines Pigmentes,
• B) 1 bis 60 Gew.-% einer Zusammensetzung, im Wesentlichen enthaltend das Mischungsprodukt von
• i) 95 bis 5 Gew.-% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids, mit
• ii) 5 bis 95 Gew.-% eines nicht hydrierten Keton-Aldehyd-Harzes, und
• iii) 0 bis 80 Gew.-% mindestens eines Lösemittels, wobei die Summe der Gewichtsangaben von Komponente i) bis iii) 100 Gew.-% beträgt,
• C) 0 bis 50 Gew.-% mindestens eines anorganischen Füllstoffes,
• D) 1 bis 40% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids,

wobei die Summe der Gewichtsangaben der Komponenten A), B, C) und D) 100 Gew.-% beträgt,
dadurch gekennzeichnet, dass
die Zusammensetzung aus dem Pigment A), der Zusammensetzung B) und gegebenenfalls dem anorganischen Füllstoff C) und gegebenenfalls dem blockcopolymeren, styrenoxidhaltigen Polyalkylenoxid ohne Zuhilfenahme eines organischen Lösemittels und/oder Wasser in einem geeigneten Aggregat dispergiert wird.The invention also provides a process for the preparation of universal pigment preparations, essentially containing

• A) 40 to 99% by weight of at least one pigment,
• B) 1 to 60% by weight of a composition substantially containing the product of the mixture of
• i) 95 to 5 wt .-% of at least one block copolymer, styrene oxide-containing polyalkylene oxide, with
• ii) from 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and
• iii) 0 to 80% by weight of at least one solvent, the sum of the weights of components i) to iii) being 100% by weight,
• C) 0 to 50% by weight of at least one inorganic filler,
• D) 1 to 40% of at least one block copolymeric, styrene oxide-containing polyalkylene oxide,

the sum of the weights of components A), B, C) and D) being 100% by weight,
characterized in that
the composition of the pigment A), the composition B) and optionally the inorganic filler C) and optionally the block copolymeric, styrene-containing polyalkylene oxide without the aid of an organic solvent and / or water in a suitable aggregate is dispersed.

As dispersing aggregates, in particular ball mills, stirred ball mills with horizontal or vertical arrangement or radial agitator mills come into consideration. However, for example, a Dispermat, a Scandex mixer, a Red Devil, a single-roller chair, a three-roll mill or a bead mill can also be used. The isolation of the pigment preparation can be carried out with the usual drying devices, for example in a fluidized bed, a spray dryer, a belt dryer or a vacuum dryer. The deagglomerating in the context of the preparation of the Pigmentzube invention agglomerates contained therein, for example by means of hammer mills, pin mills, impact mills or classifier mills, but may also be integrated into the drying process, for. B ,. in the form of a Mahltrocknung.

The Universal pigment preparations according to the invention can in all known in the art solvent-containing, solvent-free or aqueous 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 non-blocked polyisocyanate resins as crosslinkers.

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.-% einer Zusammensetzung, im Wesentlichen enthaltend das Mischungsprdukt von
• i) 95 bis 5 Gew.-% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids, mit
• ii) 5 bis 95 Gew.-% eines nicht hydrierten Keton-Aldehyd-Harzes, und
• iii) 0 bis 80 Gew.-% mindestens eines Lösemittels, wobei die Summe der Gewichtsangaben von Komponente i) bis iii) 100 Gew.-% beträgt,
• C) 0 bis 50 Gew.-% mindestens eines anorganischen Füllstoffes,
• D) 1 bis 40% mindestens eines blockcopolymeren, styrenoxidhaltigen Polyalkylenoxids,

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

• A) 40 to 99% by weight of at least one pigment,
• B) 1 to 60% by weight of a composition substantially containing the mixture product of
• i) 95 to 5 wt .-% of at least one block copolymer, styrene oxide-containing polyalkylene oxide, with
• ii) from 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and
• iii) 0 to 80% by weight of at least one solvent, the sum of the weights of components i) to iii) being 100% by weight,
• C) 0 to 50% by weight of at least one inorganic filler,
• D) 1 to 40% of at least one block copolymeric, styrene oxide-containing polyalkylene oxide,

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

The Universal pigment preparations according to the invention 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 aqueous, solvent-based or solvent-free Applications such as powder coatings become coating systems obtained having a high tinting strength, have a high gloss and a good flocculation stability.

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

Examples

1) Preparation of a Styrenoxidhaltigen Polyalkylene oxide (component B) i), not according to the invention)

336.4 g (2.34 mol) of trimethylcyclohexanol and 16.3 g (0.23 mol) of potassium methylate were placed in a reactor. After thorough purge with pure nitrogen was heated to 110 ° C, and there were 308.2 g (2.554 mol) of styrene oxide added within one hour. After two additional hours, the addition of the styrene oxide was complete, recognizable by a residual content of styrene oxide, which was <0.1 wt .-% according to gas chromatogram. Subsequently, 339.2 g (7.71 mol) of ethylene oxide were metered into the reactor so quickly that the internal temperature did not exceed 120 ° C. and the pressure did not exceed 6 bar. After complete introduction of the ethylene oxide, the temperature was maintained at 115 ° C until a constant gauge pressure indicated the end of the postreaction. Finally, at 80 to 90 ° C, the unreacted residual monomers were removed in vacuo. The product obtained was neutralized with the aid of phosphoric acid and the water was removed by distillation, and the resulting potassium phosphate was removed by filtration together with a filter aid. The molecular weight from the determination of the hydroxyl number with an assumed functionality of 1 was M = 467 g / mol.

2) Preparation of a ketone-aldehyde resin (Component B) ii), not according to the invention)

176.7 g 4-tert-butylcyclohexanone, 481.7 g of 3,3,5-trimethylcyclohexanone, 112.4 g of cyclohexanone and 373.1 g of a 30 wt .-% formalin solution were submitted and to 60 ° C. heated. Thereafter, 114.5 g of a 50 wt .-% sodium hydroxide solution within dropped from 15 min to 80 ° C heated. Subsequently, 200.0 g of the formalin solution was added dropwise within 90 min and 4 hours under reflux at 85 ° C held. The resulting resin was added after the addition of glacial acetic acid Washed water neutral. Distillation resulted in a light yellow, brittle Resins with a softening point of 85 ° C.

3) Preparation of the composition B) (not according to the invention)

500 g of the styrene oxide-containing polyalkylene oxide from Example 1) and 500 g of the ketone-aldehyde resin Example 2) were added with stirring at 80 ° C mixed together. The product was clear and had a viscosity of 88810 at 23 ° C mPa s.

4) 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 component B) from example 3) were dissolved in 560 g of water and 76.5 g ULTRA Talc 609 (from Barretts Minerals Inc.) was added. The talcum / resin mixture was added to the pigment presscake and dispersed in a dissolver. The pigment dispersion was dried in a drying cabinet and micropulverized.

5) 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 Ketone / aldehyde resin 2) in methoxypropylacetate and 187 g Disperbyk 163 (from Byk-Chemie) and 1 mm glass beads in volume ratio 1 : 1 added. The mixture was dispersed in Dispermat CV for 80 minutes at 3000 rpm.

6) 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

7) Production of the Inventive Coating Compositions

For the preparation of coating materials, the pigment preparations 4) and 5) were initially charged and the white stock paint 6) 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 6) 150.0 g 150.0 g Black, solid pigment preparation from 4) 3.2 g - Black pigment preparation from 5) - 4.2 g butylglycol 3.0g 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 66 67 Cross-hatching after 28 d 0 0-1 Erichsen cupping (mm) after 28 d 6.5 6.5 Gloss 20 ° / 60 ° after 28d 78/89 76/88 Glossy haze after 28 d 47-51 50-52 ΔE rub out 0.96 1.08

The exemplified coating composition based on the Universal pigment preparation according to the invention and a solvent-containing, white Alkyd paint possessed a high Gloss and good mechanical and coloristic properties. These Properties were based on a coating composition a solvent-containing pigment preparation comparable.

Claims (26)

Universal pigment preparations, essentially containing A) 40 to 99% by weight of at least one pigment, B) From 1% to 60% by weight of a composition substantially containing the mixture product of i) 95 to 5 wt .-% of at least one block copolymers, styrene oxide-containing polyalkylene oxide, With ii) From 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and iii) 0 to 80% by weight of at least one solvent, where the sum the weight data of component i) to iii) is 100% by weight, C) 0 to 50 wt .-% of at least one inorganic filler D) 1 to 40% at least one block copolymer, styrene oxide-containing polyalkylene oxide, in which the sum of the weights of components A), B), C) and D) 100 wt .-% is. Universal pigment preparations after the previous one Claim, characterized in that as component A) organic or inorganic pigments or carbon blacks alone or in mixtures be used. Universal pigment preparations after at least one of the preceding claims characterized in that, as organic pigments, azo pigments, Azomethine pigments, metal complex pigments, anthraquinoid pigments, phthalocyanine pigments, polycyclic pigments thioindigo, quinacridone, dioxazine, pyrrolo, naphthalenetetracarboxylic, perylene, indanthrone, Isoamidolin (on), isoindolinone, flavantbrone, pyranthrone or Isoviolanthrone series can be used alone or in mixtures. Universal pigment preparations after at least one of the preceding claims, characterized in that inorganic pigments are 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. Universal pigment preparations after at least one of the preceding claims, characterized in that used as carbon blacks gas blacks, Flammruße or Furnaceruße become. Universal pigment preparations according to at least one of the preceding claims, characterized in that the block copolymers contained in component B), styrene oxide-containing polyalkylene oxides i) have the general formula I: R ¹ O (SO) _a (EO) _b (PO) _c (BO) _d R ² I where R ^{1 is} a straight-chain or branched or cycloaliphatic radical having 8 to 13 carbon atoms, R ² = hydrogen, an acrylic radical, alkyl radical or carboxylic acid radical having in each case 1 to 8 C atoms, SO = stryrenic oxide, EO = ethylene oxide, PO = propylene oxide, BO = butylene oxide and a = 1 to 1.9, b = 3 to 50, c = 0 to 3, d = 0 to 3, where a, c or d is other than 0 and b> = a + c + d , Universal pigment preparations after at least one of the preceding claims, characterized in that ketones with aliphatic, cycloaliphatic or aromatic hydrocarbon radicals for the preparation of in Component B) contained ketone-aldehyde resins ii). Universal pigment preparations according to at least one of the preceding claims, characterized gekenn characterized in that as ketones for the preparation of the ketone-aldehyde resins contained in component B) ii) acetone, acetophenone, methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclohexanone, 4-tert-amylcyclohexanone, 2 sec. Butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone, 3,3,5-trimethylcyclohexanone, cyclopentanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, Cycloheptanone, cyclooctanone or cyclododecanone can be used. Universal pigment preparations after at least one of the preceding claims, characterized in that phenols and / or urea or its Derivatives for the preparation of the ketone-aldehyde resins contained in component B) ii) are included. Universal pigment preparations after at least one of the preceding claims, thereby in that contained in component B) not hydrogenated ketone-aldehyde resins ii) I. 40 to 100 mol%, based on all ketones used, at least one alkyl-substituted Cyclohexanone having one or more alkyl radicals having 1 to 8 carbon atoms, II. 0.8 to 2.0 mol of at least one aliphatic aldehyde, based to 1 mol of all ketones used and III. 0 to 60 mol%, based on all ketones used, other ketones with aliphatic, cycloaliphatic, aromatic hydrocarbon radicals, wherein these same or different and in turn with the said hydrocarbon radicals may be substituted in the hydrocarbon chain as well as optionally phenols and / or urea or its derivatives. Universal pigment preparations after at least one of the preceding claims, characterized in that as cyclohexanones I. 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone be used. Universal pigment preparations after at least one of the preceding claims, characterized in that as the aldehyde component in general and as II. unbranched or branched aldehydes, such as. B. formaldehyde, Acetaldehyde, n-butyraldehyde and / or iso-butyraldehyde, valeric aldehyde and Dodecanal be used. Universal pigment preparations according to claim 12, characterized in that the formaldehyde is used. Universal pigment preparations after at least one of the preceding claims, characterized in that as ketone component III. Acetone, acetophenone, Methyl ethyl ketone, heptanone-2, pentanone-3, methyl isobutyl ketone, cyclopentanone, Cyclohexanone, cyclododecanone, mixtures of 2,2,4- and 2,4,4-trimethylcyclopentanone, Cycloheptanone and cyclooctanone can be used. Universal pigment preparations after at least one of the preceding claims, characterized in that the mixing ratio of the block copolymers, styrene oxide-containing polyalkylene oxides i) and the ketone-aldehyde resins ii) is 95: 5 to 5: 95. Universal pigment preparations after at least one of the preceding claims, characterized in that as solvent iii) water is. Universal pigment preparations after at least one of the preceding claims, characterized in that as solvent iii) at least one organic solvent is included. Universal pigment preparations after at least one of the preceding claims, characterized in that as solvent iii) at least one Alcohol, ester, ketone, ether, glycol ether, aromatic hydrocarbon, hydroaromatic hydrocarbon, halohydrocarbon, terpene hydrocarbon, aliphatic Hydrocarbon, ester alcohol, dimethylformamide or dimethyl sulphoxide, is contained alone or in mixtures. Universal pigment preparations after at least one of the preceding claims, characterized in that as component C) compounds Base of kaolin, talc, mica, other silicates, quartz, Christobalite, Wollastonite, perlite, diatomaceous earth, fiber fillers, aluminum hydroxide, Barium sulfate or calcium carbonate can be used. Universal pigment preparations according to at least one of the preceding claims, characterized in that as component D) block copolymers, styrene oxide-containing polyalkylene oxides i) are used which have the general formula I: R ¹ O (SO) _a (EO) _b (PO) _c (BO) _d R ² I where R ^{1 is} a straight-chain or branched or cycloaliphatic radical having 8 to 13 carbon atoms, R ² = hydrogen, an acrylic radical, alkyl radical or carboxylic acid radical having in each case 1 to 8 C atoms, SO = stryrenic oxide, EO = ethylene oxide, PO = propylene oxide, BO = butylene oxide and a = 1 to 1.9, b = 3 to 50, c = 0 to 3, d = 0 to 3, where a, c or d is other than 0 and b> = a + c + d , Process for the preparation of universal pigment preparations according to at least one of the preceding claims 1 to 20, substantially containing A) 40 to 99% by weight of at least one pigment, B) From 1% to 60% by weight of a composition substantially containing as a mixture product of i) 95 to 5 wt .-% of at least one block copolymers, styrene oxide-containing polyalkylene oxide, With ii) From 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and iii) 0 to 80% by weight of at least one solvent, where the sum the weight data of component i) to iii) is 100% by weight, C) 0 to 50% by weight of at least one inorganic filler, D) 1 to 40% at least one block copolymer, styrene oxide-containing polyalkylene oxide, in which the sum of the weights of components A), B), C) and D) 100% by weight, thereby marked that a suspension of the pigment A), the Composition B) and optionally the inorganic filler C) and optionally the block copolymer, styrene oxide-containing polyalkylene oxide in an organic solvent and / or water is prepared, the suspension in a suitable Aggregate dispersed and the solid pigment preparation is isolated. Process for the preparation of universal pigment preparations according to at least one of the preceding claims 1 to 20, substantially containing A) 40 to 99% by weight of at least one pigment, B) From 1% to 60% by weight of a composition substantially containing the mixture product of i) 95 to 5 wt .-% of at least one block copolymers, styrene oxide-containing polyalkylene oxide, With ii) From 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and iii) 0 to 80% by weight of at least one solvent, where the sum the weight data of component i) to iii) is 100% by weight, C) 0 to 50% by weight of at least one inorganic filler, D) 1 to 40% at least one block copolymer, styrene oxide-containing polyalkylene oxide, in which the sum of the weights of components A), B), C) and D) 100% by weight, thereby marked that the composition of the pigment A), the composition B) and optionally the inorganic filler C) and optionally the block copolymer, styrene oxide-containing polyalkylene oxide without the aid of an organic solvent and / or water in a suitable aggregate is dispersed. A process for the preparation of universal pigment preparations according to claim 21 or 22, characterized in that the suspension in a ball mill, a stirred ball mill, a radial stirring mill, a Dispermat, a Scandex mixer, a Red Devil, a Einwalzenstuhl, a three-roll mill or a bead mill is dispersed. Process for the preparation of universal pigment preparations according to at least one of claims 21 to 23, characterized in that the solid pigment preparation in a fluidized bed, a spray dryer, a belt dryer or a vacuum dryer is isolated. Process for the preparation of universal pigment preparations according to at least one of claims 21 to 24, characterized in that the solid pigment preparation after their isolation in hammer mills, Pin mills, impact mills or classifier mills is deagglomerated. Use of universal pigment preparations according to at least one of the preceding claims 1 to 20, substantially containing A) 40 to 99% by weight of at least one pigment, B) From 1% to 60% by weight of a composition substantially containing the mixture product of i) 95 to 5 wt .-% of at least one block copolymers, styrene oxide-containing polyalkylene oxide, With ii) From 5 to 95% by weight of a non-hydrogenated ketone-aldehyde resin, and iii) 0 to 80% by weight of at least one solvent, where the sum the weight data of component i) to iii) is 100% by weight, C) 0 to 50% by weight of at least one inorganic filler, D) 1 to 40% at least one block copolymer, styrene oxide-containing polyalkylene oxide, in which the sum of the weights of components A), B), C) and D) 100% by weight, in Paints, varnishes, adhesives, inks or inks.