WO2007141090A1

WO2007141090A1 - Solid pigment preparations

Info

Publication number: WO2007141090A1
Application number: PCT/EP2007/053982
Authority: WO
Inventors: Andreas Wenning
Original assignee: Evonik Degussa Gmbh
Priority date: 2006-06-09
Filing date: 2007-04-24
Publication date: 2007-12-13
Also published as: CN101085876A; DE102006026762A1

Abstract

The invention relates to solid pigment preparations consisting of at least one pigment and a resin, to their production processes and to their use in paints, varnishes, adhesives or inks.

Description

Solid pigment preparations

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

These solid pigment preparations are used in coating materials such as, for example, paints, lacquers, adhesives, inks or printing inks for the coating of objects from, for example, As metals and plastics. These coating compositions are suitable for all customary application methods that are used in modern metal and plastic coating and the printing ink industry, such. As the spray application, the electrostatic spray application and printing by means of various printing processes.

Usually, colored coating materials are prepared in such a way that first of all a liquid pigment preparation is produced, which is then painted with a master paint.

In the preparation of pigment preparations, fillers and pigments are dispersed in liquid media. For this purpose, it is generally used dispersants, so as to reduce the mechanical shear forces required for effective dispersion of the solids and at the same time to achieve the highest possible fill levels. The dispersants promote the breaking up of agglomerates, wet and / or occupy the surface of the particles to be dispersed as surface-active compounds and stabilize them against undesired reagglomeration.

Wetting and dispersing agents facilitate the incorporation of pigments and fillers in the manufacture of paints and coatings, which, as important formulation constituents, substantially determine the optical appearance and the physicochemical properties of coatings. For one optimal utilization, these solids must be evenly distributed in paints and coatings, on the other hand, the once reached distribution must be stabilized. The stabilizing component is also often perceived by binder components. Such binders are also valuable components for coating materials because they contribute to faster drying and increasing the hardness of the resulting films.

For solvent-based coating materials usually solvent-based pigment preparation based on various wetting and dispersing agents are prepared, which are dissolved with various solvent-based masterbatches. For aqueous coating materials, it is customary to prepare aqueous pigment preparations based on various wetting agents and dispersants, which are then dissolved with various aqueous masterbatches.

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. As described in DE 44 04 809. EP 1 078 946 describes the use of block copolymeric polyalkylene oxides as dispersants for universal pigment preparations, which can be adjusted both aqueous and solvent-containing. The universal pigment preparations described in DE 10 2005 012 316, based on the combination of block copolymers, styrene oxide-containing polyalkylene oxides and ketone-aldehyde resins, also have 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 these liquid pigment preparations generally contain further auxiliaries, for example

Drying inhibitors, rheology additives, anti-skinning agents, biocides or agents for

Increasing the freeze resistance. To these aids and the manageability of To avoid energy and time-consuming dispersion of pigments, solid pigment preparations have been developed, which can be dissolved in water or in organic solvents by simple stirring in solution. EP 702 055 describes the dispersing of pigments in organic binders of high molecular weight, so-called stir-in pigments, for the production of colored, solvent-containing coatings. However, these pigments are not stabilized against reagglomeration, so that disturbances such as by specks are not reliably avoided.

The pigment preparations described in EP 702,062 are conditioned. 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.

EP 902 061 describes vinylpyrrolidone homopolymers or copolymers for the preparation of stir-in pigment preparations. These pigment preparations are particularly suitable for coloring aqueous industrial coatings or solvent-free plastics.

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

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. However, these resins are different from those used in the pigment preparations of the present invention. 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.

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.

The present invention has for its object to find solid pigment preparations whose composition is as simple as possible and which can be distributed by a particularly easy dispersibility in application media of various kinds, especially by simple stir-in liquid application media. By using these solid pigment preparations in solventborne or solventless applications, high color strength and flocculation stability should be present.

The object underlying the invention has surprisingly been achieved by the use of at least one non-carbonyl-hydrogenated ketone resin and / or a non-carbonyl-hydrogenated ketone / aldehyde resin in combination with at least one pigment.

Surprisingly, it has been found that such solid pigment preparations can be easily incorporated into solvent-based or solvent-free coatings. 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. The invention relates to solid pigment preparations, essentially containing

A) 40 to 99% by weight of at least one pigment,

B) 1 to 60% by weight of at least one non-carbonyl-hydrogenated ketone resin and / or one non-carbonyl-hydrogenated ketone / aldehyde resin,

C) 0 to 50% by weight of at least one inorganic filler,

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

As component A) it is possible to use organic or inorganic pigments and also carbon blacks.

Suitable organic pigments are, for example, azo pigments, azomethine pigments, metal complex pigments, anthraquinoid pigments, phthalocyanine pigments, polycyclic pigments, in particular those of the thioindigo, quinacridone, dioxazine, pyrrolo, naphthalenetetracarboxylic acid, 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. Highly suitable organic pigments are those described in the Color Index. These include, for example, the group of Cl. Pigment Red 202, Cl. Pigment Red 122, Cl. Pigment red 144, Cl. Pigment Red 170, Cl. Pigment Red 177, Cl. Pigment red 179, Cl. Pigment Red 254, Cl. Pigment red 255, Cl. Pigment Red 264, Cl. Pigment Brown 23, Cl. Pigment Yellow 13, Cl. Pigment Yellow 74, Cl. Pigment Yellow 83, Cl. Pigment Yellow 109, Cl. Pigment Yellow 110, Cl. Pigment Yellow 147, Cl. Pigment Yellow 191.1, Cl. Pigment Orange 48, Cl. Pigment Orange 49, Cl. Pigment Orange 61, Cl. Pigment Orange 71, Cl. Pigment Blue 15, Cl. Pigment Blue 60, Cl. Pigment Violet 19, Cl. Pigment Violet 23, Cl. Pigment Violet 37, Cl. Pigment Green 7, Cl. Pigment green 36. Examples of suitable inorganic pigments are metal oxides, mixed metal oxides, antimony yellows, lead chromates, lead chromate sulphates, lead molybdate, ultramarine blue, cobalt blue, manganese blue, chrome oxide green, hydrated chromium oxide green, cobalt green, metal sulphides, cadmium sulphoselenides, zinc ferrites or bismuth vanadates, alone or in mixtures.

As carbon blacks, gas blacks, black carbon blacks or furnace carbon black, alone or in mixtures, can be used. These carbon blacks can additionally be post-oxidized and / or beaded.

It is also possible to use any mixtures of organic and inorganic pigments and / or carbon blacks.

In principle, all non-carbonyl-hydrogenated ketone resins and / or non-carbonyl-hydrogenated ketone / aldehyde resins are suitable as component B) in the solid pigment preparations.

Suitable ketones for the preparation of the ketone resins and ketone / aldehyde resins are all ketones, in particular 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 having one or more alkyl radicals having a total of 1 to 8 carbon atoms, individually or in admixture. As examples of alkyl-substituted cyclohexanones there may be mentioned 4-tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone, 4-tert-butylcyclohexanone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.

In general, however, all in the literature for ketone resin and ketone / aldehyde resin syntheses called suitable ketones, usually all C-H-acidic ketones, can be used. Preferred are ketone / aldehyde resins based on

Ketone acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5- Trimethylcyclohexanone and heptanone alone or in mixture and ketone resins of cyclohexanone.

As aldehyde component of the ketone / aldehyde resins are in principle unbranched or branched aldehydes, such as. As formaldehyde, acetaldehyde, n-butyraldehyde, iso-butyraldehyde, valeric aldehyde and dodecanal. In general, all the aldehydes mentioned in the literature as suitable for ketone resin syntheses can be used. Preferably, however, formaldehyde is used alone or in mixtures.

The required formaldehyde is usually used as about 20 to 40 wt .-% aqueous or alcoholic (eg, methanol or butanol) solution. Other uses of formaldehyde such. As well as the use of para-formaldehyde or trioxane are also possible. Aromatic aldehydes, such as. B. benzaldehyde may also be included in admixture with formaldehyde.

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).

Such ketone-aldehyde resins are described for example in DD 12 433, DD 123 481, DE 12 56 898, DE 13 00 256, DE 28 31 613 and DE 44 04 809.

The vinylpyrrolidone homopolymers or copolymers described in EP 902 061 have a molecular weight of 5000 to 300 000 g / mol. With a molecular weight of less than 3000 g / mol, the ketone resins or ketone / aldehyde resins used according to the invention have a significantly lower molecular weight.

As component C) also inorganic fillers can be used. They are usually powdery, practically insoluble in the application medium substances. They are predominantly made from naturally occurring minerals by mining, Purification, grinding and subsequent classification won 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 dictated 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.

Examples of suitable fillers for use in the solid pigment preparations according to the invention are those based on kaolin, talc, mica, other silicates, quartz, cristobalite, wollastonite, perlite, diatomaceous earth, fiber fillers, aluminum hydroxide, barium sulfate and / or calcium carbonate.

The invention also provides a process for the preparation of solid pigment preparations, essentially containing A) from 40 to 99% by weight of at least one pigment,

C) 0 to 50% by weight of at least one inorganic filler,

wherein the sum of the weights of the components A), B) and C) is 100% by weight, wherein a suspension of the pigment A), the ketone resin or the ketone / aldehyde resin 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. As dispersing aggregates are in particular ball mills,

Agitator ball mills with horizontal or vertical arrangement or radial agitator mills into consideration. For example, it is also possible to use a Dispermat, a Skandex mixer, a Red Devil, a single-roller chair, a three-roll chair or a bead mill. The isolation of the solid pigment preparation can be carried out with the usual drying equipment, for example in a fluidized bed, a spray dryer, a belt dryer or a vacuum dryer. The deagglomeration of the agglomerates contained therein within the scope of the preparation of the pigment preparation according to the invention takes place, for example, by means of hammer mills, pin mills, impact mills or classifier mills, but can also already be integrated into the drying process, eg. B ,. in the form of a Mahltrocknung.

The invention therefore also provides the use of solid pigment preparations, essentially containing

A) 40 to 99% by weight of at least one pigment,

C) 0 to 50% by weight 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 pigment preparations according to the invention can be incorporated in all solvent-containing and solvent-free coating systems known to the person skilled in the art, such as paints, inks, adhesives, inks or printing inks. For example, these systems may be physically drying, oxidatively drying, or otherwise reactive in 1K or 2K paints. There are a variety of physically drying resins such as nitrocellulose, polyvinyl butyral, VC copolymers, acrylates, methacrylates, cellulose esters, cellulose ethers, hydrocarbon resins, phenolic resins, rosins, maleate resins, polystyrene resins, silicone resins, rubber based paint 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. 1 K coating materials are based, for example, on (meth) acrylate, epoxy, polyvinyl acetate, polyester or polyurethane resins. These resins may also be unsaturated, ie contain acrylate or methacrylate double bonds such 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. 1 K

Coating materials are also those based on hydroxyl-containing polyacrylate or polyester resins with melamine resins or blocked polyisocyanate resins as crosslinkers. 2K coating materials are, for example, those based on polyepoxide systems or of hydroxyl-containing polyacrylate or polyester resins with non-blocked polyisocyanate resins as crosslinkers.

All auxiliary agents and additives known to the person skilled in the art can be used in the coating systems. These include, for example, defoamers, deaerators, rheology aids, surface additives, the z. Lubricity, scratch resistance, anti-blocking, flow and gloss, substrate wetting additives, driers, stabilizers or biocides.

The pigment preparations according to the invention are solid substances and are present as powder, preferably as micropowder. They are characterized by a particularly easy dispersibility in application media of various kinds, especially by simple stir-in in liquid application media from. By using these solid pigment preparations in solventborne or solventless applications such as powder coatings Coating systems obtained which have a high color strength and a high gloss.

The following examples are intended to further illustrate the invention but not to limit its scope:

Examples

1) Preparation of a ketone / aldehyde resin (not according to the invention) 176.7 g of 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 initially charged and heated to 60 ⁰ C. Thereafter, 114.5 g of a 50 wt .-% sodium hydroxide solution were added dropwise within 15 min and heated to 80 ⁰ C. Subsequently, 200.0 g of the formalin solution was added dropwise within 90 min and held at 85 ^° C. under reflux for 4 hours. The resulting resin was washed neutral with water after addition of glacial acetic acid. Distillation resulted in a light yellow, brittle resin with a softening point of 85 ^° C.

2) Preparation of the Solid Pigment Preparation According to the Invention 380 g of special black 4 (CI Pigment Black 7 from Degussa AG) were stirred with 520 g of water to give an aqueous presscake. In a separate container, 467 g of ketone / aldehyde resin 1) was dissolved in 467 g of ethanol and 76.5 g ULTRA TaIc 609 (from Barretts Minerals Inc.) added. The talcum / resin mixture was added to the pigment presscake and dispersed in a dissolver. The pigment dispersion was dried in a drying oven 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 the ketone / aldehyde resin 1) in methoxypropylacetate and 187 g of Disperbyk 163 (ex

Byk-Chemie) 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 solvent-borne base lacquer (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 min at 2400 U / min and a surface temperature of 25 ⁰ 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

5) Production of the Inventive Coating Compositions

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

The coating composition based on the solid pigment preparation according to the invention and a solvent-containing white alkyd paint exhibited a high gloss and good mechanical and coloristic properties. These properties were with a

Coating composition comparable on the basis of a solvent-containing pigment preparation.

Claims

claims:

1. Solid pigment preparations, essentially containing A) 40 to 99 wt .-% of at least one pigment, B) 1 to 60 wt .-% of at least one non-carbonyl-hydrogenated ketone resin and / or a non-carbonyl-hydrogenated ketone / aldehyde resin, C ) 0 to 50% by weight of at least one inorganic filler,

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

2. Solid pigment preparations according to claim 1, characterized in that as component A) organic or inorganic pigments or carbon blacks, alone or in mixtures, are included.

3. Solid pigment preparations according to 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 of the thioindigo, quinacridone, dioxazine, pyrrolo, naphthalenetetracarboxylic acid, perylene, indanthrone, isoamidoline (on), isoindolinone, flavanthrone, pyranthrone or isoviolanthrone series, alone or in mixtures.

4. Solid pigment preparations according to at least one of the preceding claims, characterized in that as inorganic pigments metal oxides, mixed metal oxides, Antimongelb, Bleichromate, Bleichromatsulfate, Bleimolybdate, ultramarine blue, cobalt blue, manganese blue, chrome oxide green, hydrated Chromoxidgrün,

Cobalt green, metal sulfides, cadmium sulfoselenides, zinc ferrites or bismuth vanadates, alone or in mixtures.

5. Solid pigment preparations according to at least one of the preceding claims, characterized in that as carbon blacks gas blacks, flame blacks and / or Furnaceruße are included.

6. Solid pigment preparations according to at least one of the preceding claims, characterized in that contained in the ketone resins and ketone / aldehyde resins of component B) C-H-acidic ketones.

7. Solid pigment preparations according to at least one of the preceding claims, characterized in that in the ketone resins 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 having one or more alkyl radicals having a total of 1 to 8 carbon atoms, alone or in mixtures ,

8. Solid pigment preparations according to at least one of the preceding claims, characterized in that in the ketone resins and ketone / aldehyde resins of component B) A- tert-amylcyclohexanone, 2-sec-butylcyclohexanone, 2-tert-butylcyclohexanone , A-tert-butylcyclohexanone, 2-methylcyclohexanone or 3,3,5-

Trimethylcyclohexanone, alone or in mixtures are included.

9. Solid pigment preparations according to at least one of the preceding claims, characterized in that in the ketone resins and ketone / aldehyde resins of component B) acetophenone, cyclohexanone, 4-tert-butylcyclohexanone, 3,3,5- Trimethylcyclohexanone or heptanone, alone or in mixtures.

10. Solid pigment preparations according to at least one of the preceding claims, characterized in that as aldehydes formaldehyde, acetaldehyde, n-butyraldehyde, isobutyraldehyde, valeric aldehyde and dodecanal, are contained alone or in mixtures.

11. Solid pigment preparations according to at least one of the preceding claims, characterized in that formaldehyde is contained.

12. Solid pigment preparations according to at least one of the preceding claims, characterized in that as component C) compounds selected from kaolin, talc,

Mica, other silicates, quartz, cristobalite, wollastonite, perlite, diatomaceous earth, fiber fillers, aluminum hydroxide, barium sulfate and / or calcium carbonate.

13. A process for the preparation of solid pigment preparations, essentially containing

A) 40 to 99% by weight of at least one pigment,

B) 1 to 60% by weight of at least one non-carbonyl-hydrogenated ketone resin and / or a non-carbonyl-hydrogenated ketone / aldehyde resin, C) 0 to 50% by weight of at least one inorganic filler,

wherein the sum of the weights of components A), B) and C) is 100 wt .-%, wherein a suspension of the pigment A), the ketone resin or the ketone / aldehyde resin B) and optionally the inorganic filler C ) is prepared in an organic solvent and / or water, the suspension dispersed in a suitable aggregate and the solid pigment preparation is isolated.

14. A process for the preparation of solid pigment preparations according to claim 13, characterized in that the suspension is dispersed in a ball mill, a stirred ball mill, a radial agitator mill, a Dispermat, a Skandex mixer, a Red Devil, a Einwalzenstuhl, a three-roll mill or a bead mill becomes.

15. A process for the preparation of solid pigment preparations according to at least one of claims 13 to 14, characterized in that the solid pigment preparation is isolated in a fluidized bed, a spray dryer, a belt dryer or a vacuum dryer.

16. A process for preparing solid pigment preparations according to any one of claims 13 to 15, characterized in that the solid pigment preparation after its isolation in hammer mills,

Pin mills, impact mills or classifier mills is deagglomerated.

17. Use of solid pigment preparations, essentially containing A) 40 to 99 wt .-% of at least one pigment, B) 1 to 60 wt .-% of at least one non-carbonyl-hydrogenated ketone resin and / or a non-carbonyl-hydrogenated ketone / aldehyde resin , 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.