Indian Patents. 214096:A PROCESS FOR THE PREPARATION OF PIGMENT IN GRANULE FORM.

Title of Invention	A PROCESS FOR THE PREPARATION OF PIGMENT IN GRANULE FORM.
Abstract	PIGMENT PREPARATION IN GRANULE FORM COMPRISING A RESIN OR RESIN MIXTURE , ONE OR MORE EFFECT PIGMENTS AND, WHERE APPROPRIATE, ADDITIVES, WHEREIN THAT THE GRANULES COMPRIOSE 3-10% BY WEIGHT OF WATER OR A SOLVENT OR SOLVENT MIXTURE HAVING A VAPOUR PRESSURE OF 0.001 -40 hPa (20oC).

Full Text	(Pigment preparation in granule form) The invention relates to pigment preparations in granule form comprising one or more resins, one or more effect pigments and, where appropriate, additives, the granules being notable for comprising 3-10% by weight of water or a solvent or solvent mixture having a vapour pressure at 20°C of from 0.001 to 40 hPa. In industrial processes, pigments are often not employed in the form of dry powders, since such powders produce dust, which leads to heightened requirements in terms of workplace safety. In many cases, furthermore, when introducing powders into plastics, basecoat systems, etc., agglomeration of the pigment powder is observed. Homogeneous distribution of the pigment in the respective matrix is frequently difficult if not impossible to achieve. In order to obtain the lustre effect typical of pearl lustre pigments in a formulation, extremely uniform distribution and orientation of the pearl lustre pigment particles in the binder is a necessity. In applications, pigment granules feature a markedly reduced dust nuisance and better free-flow properties than pulverulent pigment preparations, and are therefore garnering increasing interest. The additional treatment of the pigments with a resin greatly enhances the performance properties of the pigments. EP 0 134 676 B1 discloses a process for preparing non- dusting metal pigment compositions, in which the paste is prepared by mixing an organic binder medium and a metal pigment with an organic liquid vehicle. After the end of the preparation process, the organic liquid vehicle is removed from the coherent paste and the resulting solid mass is divided into particles. Solvent-free, free-flowing granules comprising pearl lustre pigments and a binder and also additives, where appropriate, are claimed, furthermore, in EP 0 803 552 B1. The granules described therein are especially suitable as precursors for printing inks. The prior art granules which have been largely freed from solvent during the preparation process, however, are comparatively difficult to dissolve again in the printing ink, and/or give rise to difficulties on dispersing. For the homogenization of the pearl lustre pigments from the granules in the formulation that is to be prepared, mechanical forces are required, which may in turn disrupt the platelets of the pearl lustre pigments, thereby adversely affecting the optical properties of the pigments. It is an object of the present invention to provide effect pigment formulations in the form of solid particle forms which do not have the abovementioned disadvantages and which possess a markedly higher dissolution rate in binder systems than granules which have been largely freed from solvent. It has surprisingly been found that the dissolution rate of granules comprising resins and effect pigments, such as pearl lustre pigments, for example, resins and, where appropriate, additives in printing inks or coating materials can be significantly increased if the granules are not freed completely from the solvent but instead still contain a precisely defined amount of solvent. The invention accordingly provides pigment formulations in solid particle form comprising effect pigments, resins and, where appropriate, additives, characterized in that they contain 3-10% by weight, based on the granules, of a solvent which is non-volatile at room temperature: The chosen solvent or solvent mixture is selected so that it has a vapour pressure at 20°C of from 0.001 to 40 hPa. The granules of the invention are notable for an increased dissolution rate when incorporated by stirring into a binder system. Consequently, subsequent homogenization of the formulation that is to be prepared is made easier, since lower mechanical forces are needed to dissolve the granules. The introduction of foam into aqueous binder systems, and the risk of fracture of particularly coarse pigment fractions, are considerably reduced. Below the abovementioned solvent content ( the solvation or solubility of the granules, especially in solvent-containing and radiation-curing extenders, is greatly reduced. Moreover, the precise metering of the solvent content in the granules leads to better wetting of the pigment particles. The granules of the invention are non-dusting, free- flowing, are much quicker to incorporate into commercially available binder systems than the prior art granules, and are compatible in the said systems. In particular the products are compatible with aqueous, solvent-containing and solvent-free printing ink and coating systems. The inks and coating materials prepared using the granules are suitable for gravure printing, flexographic printing, screen printing, offset overprint varnish (OPV) and also for the various coating systems in the industrial coating and automotive coating sectors. They are also suitable for colouring plastics. The pigment granules of the invention contain ? 60% by weight, preferably 70-90% by weight, in particular 80- 90% by weight, of effect pigments. Very particular preference is given to pigment preparations having an effect pigment content of more than 80% by weight. The percentages by weight are always based on the granules. The effect pigments referred to here are pearl lustre pigments, metallic effect pigments, multilayer pigments with transparent and opaque layers, holographic pigments, BiOCl and LCP (liquid crystal polymer) pigments. Particular preference is given to granules comprising pearl lustre pigments based on platelet-shaped, transparent or semi-transparent substrates. Examples of suitable substrates are phyllosilicates, such as natural or synthetic mica or other silicatic materials, talc, sericite, kaolin and SiO2, glass, TiO2, graphite and AL2O3 platelets. Examples of the platelet-shaped substrates are those coated with rare earth metal sulfides, such as Ce2S3, titanium suboxides, titanium oxynitrides, pseudobrookite, with coloured or colourless metal oxides, such as TiO2, (rutile or anatase) Fe2O3, Fe3O4, SnO2, ZrO2, SiO2, Al2O3, Cr2O3, ZnO, CuO, NiO, Ce2O3 and other metal oxides, alone or in a mixture, in one uniform layer or in successive layers (multilayer pigments). Pearl lustre pigments are known, for example, from German patents and Patent Applications 14 67 468, 19 59 998, 20 09 566, 22 14 454, 22 15 191, 22 44 298, 23 13 331, 25 22 572, 31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355, 32 11 602, 32 35 017 and P 38 42 330 and are available commercially, e.g. under the brand name Iriodin® from Merck KGaA, Darmstadt, Germany. Multilayer pigments based on mica are sold, for example, by Merck KGaA or by EM Industries under the brand name Timiron® Splendid Copper, Timiron® Splendid Gold, Timiron® Splendid Green, Iriodin® Solargold or Dichrona® Splendid. Particularly preferred are multilayer pigments based on mica having a TiO2-SiO2-TiO2 layer sequence. Particularly preferred pigment granules comprise TiO2-, Fe2O3- or TiO2/Fe2O3-coated mica, Al2O3 or SiO2 platelets. The SiO2 platelets may be coated, for example, as described in WO 93/08237 (wet-chemical coating) or DE-A 196 14 637 (CVD process) . Al2O3 platelets are known, for example, from EP 0 763 573 A1. Platelet- shaped substrates coated with one or more rare earth metal sulfides are disclosed, for example, in DE-A 198 10 317. Also suitable are metallic effect pigments, especially aluminium flakes modified for aqueous and solvent- containing systems, as sold by Eckart under the brand name Rotovario Aqua or Stapa Hydroxal® for aqueous applications, and also Variocrom® and Paliocrom® pigments from BASF, including in particular those from the Laid-Open Specifications EP 0 681 009 A1, EP 0 632 110 A1, EP 0 634 458 A1, and also LCP pigments (liquid crystal polymers). Examples of suitable effect pigments from BASF are Variocrom ED 1478, Variocrom ED 1479 and Variocrom ED 1480. Likewise suitable, furthermore, are all holographic pigments known to the person skilled in the art, and also platelet-shaped pigments which have metal layers. Pigments of this kind are sold, among others, by Flex, for example, under the brand names Chromaflair Red/Gold 000, Chromaflair Gold/Silver 080, Chromaflair Green/Purple 190 and Chromaflair Silver/Green 060. The Chromaflair pigments with a particle size of about 11-13 µm consist of an opaque aluminium core and a magnesium fluoride layer of varying thickness which generates the later interference colour of the resulting pigment. Additionally, a semi-translucent chromium layer is applied as the outermost layer. The pigment granules of the invention may comprise one or more effect pigments. In many cases it is possible by using at least two different effect pigments to obtain special colour effects and lustre effects. Preferred pigment granules comprise one or two, or else three, effect pigments, especially those pigments which are based on mica and/or SiO2 platelets. Also possible are blends of the effect pigments with organic and inorganic pigments at up to 10% by weight based on the granules, in which case the total amount of pigment ought not to exceed 90% by weight, based on the granules. Blending allows colour flops to be set in a very targeted way. In particular, the addition of one or more dyes and/or organic pigments in dispersed form leads to special colour effects. It is also possible to add those substances and particles (tracers) which enable the product to be identified. As a mandatory component, the granules of the invention contain a resin or resin mixture in amounts of 4.5-30% by weight, preferably 4.5-25% by weight, in particular 4.5-20% by weight, based on the pigment granules. The acid number of the resin or resin mixture used is preferably from 90 to 350, in particular from 120 to 280 and, with very particular preference, from 150 to 270. Suitable resins include all natural, semi-synthetic and fully synthetic resins or resin mixtures which are known to the person skilled in the art and in which effect pigments are commonly used. In particular, mention may be made here of ketone resins, aldehyde resins, cellulose and cellulose derivatives, such as alkylcellulose, hydroxycelluloser hydroxyalkylcellu- lose, cellulose acetobutyrate, cellulose nitrate, rosins, polyacrylate or polymethacrylate resins, alkyd resins, polyester resins, polyphenol resins, melamine resins, polyterpene, polyvinyl, polyvinyl chloride and polyvinylpyrrolidone resins, polystyrenes, polyolefins, epoxy resins, polyurethanes, urea, aromatic- formaldehyde resins, carbamic acid, sulfonamide and sulfo polyesters. Particularly good dispersibility and redispersibility of the granules of the invention has been found if the resins used comprise modified rosins, especially styrene- and/or maleic-modified rosins, ketone and aldehyde resins, cellulose and/or cellulose derivatives, sulfo polyesters, styrene-modified maleates, polyacrylate resins or polyraethacrylate resins, and styrene-modified polyacrylate resins. Particular preference is given to rosins which carry carboxyl groups, such as maleic- and fumaric-acid- modified rosins. Modified rosins are widely available on the market and are sold, for example, by Kraemer under the brand name Erkamar. Preference is also given to styrene-modified polyacrylate resins, sold for example under the brand name Morez by Morton. A key constituent of the granules of the invention is the solvent or - solvent mixture, which is present in amounts of ? 3% by weight, but at most up to 10% by weight, in the granules of the invention. The granules preferably contain 3-7.5% by weight, especially 3-5.0% by weight, of solvent, based on the granules. The solvent component in the granules must in each case be properly adapted to the resin system used. For preparation it is possible to use water and also all non-volatile organic solvents. Examples of suitable solvents are aromatic solvents, e.g. toluenes, petroleum spirits, xylenes, mineral oils, vegetable oils, glycol ethers, such as propylene glycol monoethyl ether, propylene glycol monoethyl ether or diols, such as ethylene glycol and propylene glycol or polyether diols, aliphatic triols and tetraols having from 2 to 6 carbon atoms, such as trimethylolethane, trimethylol- propane, glycerol, 1,2,4-butanetriol and 1,2,6- hexanetriol, alcohols, ketones, esters, and all other solvents from other classes of compound, or a mixture of two or three of the aforementioned solvents. Particular preference is given to solvents having a boiling point > 35°C, especially > 70°C. It is preferred to use those solvents which are of medium or high viscosity. Particular preference is given to solvents which are readily miscible with water. It is important that during the preparation the solvent component includes at least one solvent or solvent mixture which has a vapour pressure at 20°C of from 0.001 to 40 hPa, preferably from 0.001 to 30 hPa. Particularly preferred solvents are water, polyalkylene glycol, glycol ethers, diols, aliphatic triols having 2-6 carbon atoms, glycerol, 1,2,4-butanetriol, 1,2,6- hexanetriol or a mixture of two or three of the aforementioned solvents. The vapour pressures of the suitable solvents may easily be determined by the person skilled in the art or looked up in the Handbook of Chemistry and Physics, 71st Edition, 1990-1991, David R. Lide, CRC Press, chapter 6-48. Particular preference is given to polyalkylene glycols, toluene (29 hPa), xylene (10 hPa), 1,2-ethanediol (0.053 hPa), 1,2,3-hexanetriol (0.01 hPa), 1,2,3- propanetriol (0.001 hPa), and water (23 hPa). The water may also contain dissolved sorbitol or urea. Preferred polyalkylene glycols are polyethylene glycol (0.1 hPa) and ethylene glycol monobutyl ether (0.8 hPa) (vapour pressures at 20°C indicated in brackets in each case are from, the Handbook of Chemistry and Physics). As a further component, the granules preferably comprise one or more neutralizing agents. Particularly suitable agents are the bases: common in the coatings sector, such as urea, urea derivatives, ammonia, amino alcohols, such as 2-amino-2-methyl-l-propanol, alkali metal hydroxides, such as KOH or NaOH, amines, the latter in the case of granules for aqueous applications preferably being organic amines of low molecular mass which are non-volatile or possess a low volatility at room temperature. In general, the pigment granules of the invention contain from 0-05 to 10% by weight of neutralizing agent, preferably from 1 to 7% by weight, in particular from 1.5 to 5% by weight, based on the pigment granules. The granules of the invention may further comprise a modifier, as a further component, in amounts of from 0.05 to 10% by weight, preferably from 0.05 to 6% by weight, in particular from 0.05 to 3% by weight. The modifier used is in particular a polyalkylene oxide or polyalkylene oxide derivative, whose purpose is to enhance the strength of the granules and also their compatibility. If necessary, the addition of a redispersing agent in the form of bulky particles, such as fibres or spherical particles, for example, prevents the effect pigments treated in accordance with the process of the invention from lying on top. of one another to a notable extent as a result of steric repulsion and so exerting strong adhesion. The effect of this is that the granules of the invention are more stable and the effect pigments, after the granules have been introduced into the paint, printing ink or coating system, settle more slowly - in some cases very much more slowly - and the sediment is in any case less hard, and that no problems occur when the sediment is reagitated. The redispersing agent is used preferably in amounts of from 0 to 5% by weight, in particular from 0.05 to 3% by weight, based on the granules. All organic and inorganic fibres having a fibre length of 0.1-20 µm that are known to the person skilled in the art may be used. Suitable particles are, in particular, all synthetic fibres, e.g. those of polyethylene, polyacrylates, polypropylene, polyamides, cellulose fibres, inorganic fibres, including preferably silicon compounds, glass fibres and also, in particular, the condensation products of modified isocyanates and mono- and diamines. These condensation products, comprising diurea derivatives and also amino ureas containing urethane groups, are known as thixotropic agents and together with a binder are added to paints and coating materials in order to improve the running properties and the brushability. As redispersing agents it is also possible to use all diurea derivatives and urethane compounds that are known to the person skilled in the art, as are described, for example, in EP 0 198 519 and in Organic Coatings: Science and Technology, A.. Heenriga, P.J.G. von Hemsbergen, pp. 201-222, New York 1983. Particularly - suitable spherical materials are hollow glass, wax or polymer beads made of vinyl resins, nylon, silicone, epoxy resins, olefin resins, polystyrenes, and inorganic materials, such as TiO2, SiO2 or ZrO2, for example. It is preferred to use hollow beads, but also solid beads, having a particle size of from 0.05 to 150 Mm. In the granules of the invention it is particularly preferred to use hollow glass, wax or polymer beads. Spherical particles based on SiO2 in a particle range of 3-10 µm are known, for example, as materials for high-performance liquid chromatography and are sold, for example, as LiChrospher® by Merck KGaA, Darmstadt, FRG. Such materials are preferably used in monodisperse form; that is, with a substantially uniform particle size. Monodisperse spherical particles of this type based on SiO2, TiO2 and ZrO2 are known. Monodisperse SiO2, for example, may be prepared in accordance with EP 0 216 278 B1. Hollow glass beads are sold, for example, under the trade name Q-CEL by PQ Corporation, USA, or Scotchlite by 3M, Frankfurt, FRG. Additionally, the granules of the invention may comprise surface-active substances, such as alkylsilanes, for example, which may also contain a further functional group, or saturated or unsaturated fatty acids or fluorosurfactants. Particular preference is given to using silane compounds of the formula (CnH2n+1)Si(OCmH2m+1)3, where n is 1-30 and m is 1-10, as surface-active substances. Examples of suitable silane compounds are n-hexyldecyltriethoxysilane and n-octyl- decyltriethoxysilane {Si 116 and Si 118 from Degussa AG, Frankfurt) and also the corresponding fluoroalkyl- silanes. As surface-active substances it is also possible to use the saturated and unsaturated fatty acids, such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid, for example, and also fatty acid mixtures. The surface-active reagent may also comprise a mixture of silane, fatty acids and/or surfactants. The granules may contain from 0.1 to 5% by weight, preferably from 0.2 to 3% by weight and in particular from 0.5 to 2% by weight of surface-active substances, based on the pigment. For the preparation of the granules, the pigments, the resin and/or the resin mixture, and also the additives, where present, are mixed with the solvent. The fraction of the solvent at the beginning of the preparation is between 20-40% by weight, preferably between 25-35% by weight. During the preparation of the granules the resin and/or resin mixture and also optionally further additives are preferably premixed with the solvent before being added to the pigment. This produces intensive contact between pigment and the substances required for the granulation, which at the same time ensures more uniform covering of the pigment surface. Subsequently, this mixture is gently homogenized. Preferably, the pigment is introduced as the initial charge and is first pasted up, with stirring, with the solvent containing the resin and, if desired at this stage, the modifier; subsequently, a further solution consisting of solvent and additives is added. During or after its production, further customary additives may be added to this pigment preparation, examples being defoamers, wetting agents, anti-settling agents, levelling agents, emulsifiers, siccatives or thixotropic agents. These are auxiliaries which are customary in the coatings industry and may be present in the granules of the invention in an amount of from 0 to 10% by weight. Mention is made here in particular of succinate derivatives, examples being those as sold by Henkel under the brand name Hydropalat 875. To prepare the granules, the moist pigment preparation is extruded or compacted into a compact particle form by other methods known to the person skilled in the art, such as by tableting, briquetting, pelletizing, granulating, spray-granulating or fluidized-bed granulating, and then dried under precisely controlled conditions. In the course of the drying operation, the solvent content of the granules is measured continuously. Depending on the solvent used, the drying process . takes place at temperatures of from 60 to 150°C, preferably at from 60 to 120°C, and may where appropriate take place under reduced pressure, preferably at 80-100 mbar. The duration of drying depends on the batch size of the preparation to be dried, its throughput in the course of drying, and the solvent used, but is generally 0.5-24 h, preferably 1-18 h. As soon as the granules have a residual solvent moisture content of ? 3% by weight, but = 10% by weight, the drying operation is halted. Finally, the granules are classified where necessary. The term "granules" as used herein embraces all possible solid particle forms, such as pellets, chips, briquettes, tablets, etc. The particle sizes of the granules are situated within the range from 0.1 to 150 mm, preferably from 0.1 to 20 mm, in particular from 0.1 to 6 mm. The determination of the residual solvent moisture content in the course of the preparation process takes place using a Sartorius MA 30 moisture analyzer, which works on an infrared basis. Following calibration, the water content is measured. Where further solubility enhancers are to be measured, this is done in accordance with the principle of differential weighing, since the substances to be analysed may be expelled together with the water above the previously calibrated temperature. There remains only the fraction of polymeric substance/resin and the effect pigment. When measuring the water content using the Sartorious MA 30 moisture analyzer, the following parameters may be chosen in order to find the result: Initial sample mass: 4-5 g of unground substance- Temperature: 135-160°C Time setting: 12-20 minutes Result indication: 0-100% (solvent content). The granules of the invention may be used for diverse applications. They are preferably used in coating systems from the sectors of printing, especially overprint varnishing, offset overprint varnishing, gravure, flexographic and screen printing. With particular preference, the granules as precursors for coating materials are applied to any desired substrate materials, examples being metals such as iron, steel, aluminium, copper, bronze, plastic, brass and also metal foils, and also glass, ceramic and concrete, and also wood, e.g. furniture, clay, textile, paper, packaging materials, e.g. plastic containers, films or boards, or to other materials for decorative and/or protective purposes. Furthermore, the granules of the invention are suitable in formulations for producing security features. Accordingly, the invention also provides for the use of the granules of the invention in formulations such as paints, printing inks, security printing inks, coating materials, powder coating materials, coatings such as industrial and automotive coatings, in plastics, and in cosmetics. The examples which follow are intended to illustrate the invention without, however, restricting it. Examples Example 1 1.1 Preparation of the granulating solution 260.0 g of DI water at 50°C are introduced as an initial charge and 72 g of Rokramar 2150 granulating resin (modified rosin from Kramer) are incorporated by means of a 4-paddle stirrer. Then 17 g of 25% ammonia solxttion are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 (from Merck KGaA) are added with stirring, followed by stirring for 5 minutes. 1.2 Preparation of the granules To prepare the granules, thorough mixing must be ensured. On the 1 kg scale, the mixture is prepared with the aid of an Eirich R02 mixer. 607 g of Iriodin® 231 (TiO2/mica pigment of particle size 5-25 urn from Merck KGaA, Germany) are placed in the mixer vessel and 393 g of granulating solution from Example 1.1.are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 µm sieve. The solvent content of the granules in the drying process is measured continuously using the Sartorius MA 30 moisture analyzer. The following parameters were chosen in order to find the result: Initial sample mass: 4-5 g of unground substance Temperature: 160°C Time setting: 20 minutes Result indication: 0-100% (solvent content). The product is abrasion-resistant and dimensionally stable and is compatible, for example, with the customary solvent-free, free- radically UV-curing Rayoflex extender varnish, 11 HF 60 (UV varnish) from Hartmann Druckfarben and with the solvent-containing extender varnish Haptobond CT 105 (based on nitrocellulose with ethanol as solvent) from Hartmann Druckfarben. The granules thus prepared also exhibit a high dissolution rate when incorporated by stirring into the said printing ink systems. Example 2 2.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as an initial charge and 66 g of Morez 300 granulating resin (polyacrylate resin from Morton) are incorporated by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-2-methyl-1-propanol solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added with stirring, followed by stirring at 300 rpm for 5 minutes. 2.2 Preparation of the granules 597 g of Iriodin® 231 (TiO2/mica pigment of particle size 5-25 mm from Merck KgaA) are placed in the mixer vessel and 403 g of granulating solution are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all. separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 µm sieve. The solvent content of the granules in the drying process is measured continuously using the Sartorius MA 30 moisture analyzer. The following parameters were chosen in order to find the result: Initial sample mass: 4-5 g of unground substance Temperature: 135°C Time setting: 12 minutes Result indication: 0-100% (solvent content). The granules obtained possess a residual moisture content of approximately 4 ± 0.5% by weight and are abrasion-resistant, dimensionally stable, compatible, and also readily soluble in the aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Example 3 3.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as an initial charge and 66 g of Morez 300 granulating resin are incorporated by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-2-methyl-l- propanol solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added with stirring, followed by stirring at 300 rpm for 5 minutes. 3.2 Preparation of the granules 597 g of Iriodin® 103 (TiO2/mica pigment of particle size 10-60 mm, Merck KGaA, Darmstadt, Germany) are introduced and 403 g of granulating solution are slowly added. At a speed of 300- 500 rpm, 19.5 g of Solcolor Green (CI PG 7) pigment preparation from MK Chemicals are added as well. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. This gives greenish pearl lustre granules having interesting colouristic properties. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The product possesses a residual moisture content of 4 ± 0.5% by weight and is abrasion-resistant, dimensionally stable, compatible, and also readily soluble in the common offset overprint varnish 350081 from Weilburger Lackfabrik. Example 4 4.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as an initial charge and 66 g of Morez 300 granulating resin are incorporated by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-2-methyl-1- propanol solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added with stirring, followed by stirring at 300 rpm for 5 minutes. 4.2 Preparation of the granules 597. g of Iriodin® 103 are placed in the mixer vessel and 403 g of granulating solution are slowly added. At a speed of 300-500 rpm, 19.5 g of Solcolor Yellow (CI PY 83) pigment preparation from MK Chemicals are added as well. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. This gives yellowish pearl lustre granules having interesting colouristic properties. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The granules possess a residual moisture content of 4 ± 1% by weight and are abrasion-resistant, dimensionally stable, compatible, and also readily soluble in the common aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Example 5 5.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as an initial charge and 66 g of Morez 300 granulating resin (polyacrylate resin from Morton) are incorporated by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-2-methyl-l-propanol solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added with stirring, followed by stirring at 300 rpm for 5 minutes. 5.2 Preparation of the granules To prepare the granules, thorough mixing must be ensured. On the 1 kg scale, the mixture is prepared with the aid of an Eirich R02 mixer. 597 g of Paliocrom® Gold L2002 from BASF AG are placed in the mixer vessel and 403 g of granulating solution are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5- 4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The solvent content of the granules in the drying process is measured continuously using the Sartorius MA 30 moisture analyzer. The following parameters were chosen in order to find the result: Initial sample mass: 4-5 g of unground substance Temperature: 135°C Time setting: 12 minutes Result indication: 0-100% (solvent content) The granules obtained possess a residual moisture content of approximately 5 ± 0.5% by weight and are abrasion-resistant, dimensionally stable, compatible, and also readily soluble in the aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Example 6 6.1 Preparation of the granulating solution 260.0 g of DI water at 50°C are introduced as an initial charge and 72 g of Rokramar 2150 granulating resin (modified rosin from Kramer) are incorporated by means of a paddle stirrer. Then 17 g of 25% ammonia solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 (from Merck KGaA) are added with stirring, followed by stirring for 5 minutes. 6.2 Preparation of the granules To prepare the granules, thorough mixing must be ensured. On the 1 kg scale, the mixture is prepared with the aid of an Eirich R02 mixer. 607 g of Colorstream® Autumn Mystery (Fe2O3-coated SiO2 platelet of particle size 5-40 mm from Merck KGaA, Germany) are placed in the mixer vessel and 393 g of granulating solution from Example 6.1 are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The product is abrasion-resistant and dimensionally stable and is compatible, for example, with the customary solvent-free, free- radically UV-curing Rayoflex extender varnish, 11 HF 60 (UV varnish) from Hartmann Druckfarben and with the solvent-icontaining extender varnish Haptobond CT 105 (based on nitrocellulose with ethanol as solvent) from Hartmann Druckfarben. The granules thus prepared also exhibit a high dissolution rate when incorporated by stirring into the said printing ink systems. Example 7 7.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as an initial charge and 66 g of Morez 300 granulating resin (polyacrylate resin from Morton) are incorporated by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-2-methyl-1-propanol solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added to the granulating solution with stirring, followed by stirring at 300 rpm for 5 minutes. 7.2 Preparation of the granules 597 g of Chromaflair Silver/Green 060 effect pigment from Flex (aluminium substrate with an MgF2 layer and an outer Cr layer, of particle size 11-13 mm) are placed in the mixer vessel and 4.03 g of granulating solution from Example 7.1 are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The solvent content of the granules in the drying process is measured continuously using the Sartorius MA 30 moisture analyzer. The following parameters were chosen in order to find the result: Initial sample mass: 4-5 g of unground substance Temperature: 135°C Time setting: 12 minutes Result indication: 0-100% (solvent content). The granules obtained possess a residual moisture content of approximately 4 ± 0.5% by weight and are abrasion-resistant, dimensionally stable, compatible, and also readily soluble in the aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Example 8 8.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as an initial charge and 66 g of Morez 300 granulating resin (polyacrylate resin from Morton) are incorporated by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-2-methyl-1-propanol solution tare added slowly and the mixture is stirred until the. granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added to the granulating solution with stirring, followed by stirring at 300 rpm for 5 minutes. 8.2 Preparation of the granules 597 g of Variocrom ED 1478 from BASF AG are placed in the mixer vessel and 403 g of granulating solution are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The solvent content of the granules in the drying process is measured continuously using the Sartorius MA 30 moisture analyzer. The following parameters were chosen in order to find the result: Initial sample mass: 4-5 g of unground substance Temperature: 135°C Time setting: 12 minutes. Result indication: 0-100% (solvent content) The granules obtained possess a residual moisture content of approximately 4 ± 0.5% by weight and are abrasion-resistant, dimensionally stable, compatible, and also readily soluble in the aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Example 9 9.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as. an initial charge and 66 g of Morez 300 granulating resin (polyacrylate resin from Morton) are incorporated within 1 minute at 300 rpm by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino- 2-methyl-1-propanol solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added to the granulating solution with stirring, followed by stirring at 300 rpm for 5 minutes. 9.2 Preparation of the granules 597 g of 610 0 010 Non-Leafing Silver (acrylic based) from Eckart (aluminium effect pigment of particle size D50 = 8 mm) are placed in the mixer vessel and 403 g of granulating solution are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The solvent content of the granules in the drying process is measured continuously using the Sartorius MA 30 moisture analyzer. The following parameters were chosen in order to find the result: Initial sample mass: 4-5 g of unground substance Temperature: 135°C Time setting: 12 minutes Result indication: 0-100% (solvent content). The granules obtained possess a residual moisture content of approximately 4 ± 0.5% by weight and are abrasion-resistant, dimensionally stable, compatible, and also readily soluble in the aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Example 10 10.1 Preparation of the granulating solution 260.0 g of DI water at 50°C are introduced as an initial charge and 72 g of Rokramar 2150 granulating resin (modified rosin from Kramer) are incorporated by means of a 4-paddle stirrer. Then 17 g of 25% ammonia solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 (from Merck KGaA) are added with stirring, followed by stirring for 5 minutes. 10.2 Preparation of the granules 607 g of Timiron® Splendid Gold from Merck KGaA or EM Industries (multilayer pigment based on mica with alternating SiO2 and TiO2 layers, of particle size 10-60 mm) are placed in the mixer vessel and 393 g of granulating solution from Example 10.1 are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The solvent content of the granules in the drying process is measured continuously using the Sartorius MA 30 moisture analyzer. The following parameters were chosen in order to find the result: Initial sample mass: 4-5 g of unground substance Temperature: 160°C Time setting: 20 minutes Result indication: 0-100% (solvent content) The product is abrasion-resistant and dimensionally stable and is compatible, for example, with the customary solvent-free, free- radically UV-curing Rayoflex extender varnish, 11 HF 60 (UV varnish) from Hartmann Druckfarben and with the solvent-containing extender varnish Haptobond CT 105 (based on nitrocellulose with ethanol as solvent) from Hartmann Druckfarben. The granules thus prepared also exhibit a high dissolution rate when incorporated by stirring into the said printing ink systems. Example 11 11.1 Preparation of the granulating solution 231.1 g of Eastek 1300 (30% sulfo polyester dispersion in water, pH = 6; density: 1.08 g/cm3; MFT: 12°C) are introduced as an initial charge and 144.3 g of DI water are stirred in using a 4- paddle stirrer. This solution is used as a granulating solution to prepare effect pigment granules. 11.2 Preparation of the granules 624.6 g of Iriodin® 231 from Merck KGaA are placed in the mixing vessel and 375.4 g of granulating solution from Example 11.1 are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granulating plate from Eirich. The wet, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5- 4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated from their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classification using a 400 mm sieve. The granules obtained are abrasion-resistant, dimensionally stable and compatible and also readily soluble in the aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Example 12: Paint Formulations consisting of 3.00% pigment granules from Example 1 1.50% Monastral green 6Y spec, (from Zeneca) 0.50% Cappoxyt yellow 4214 (from Cappelle) 0.03% FW 200 pigment black (from Degussa) 0.40% dollar aluminium Alpate 7620 NS (from Alcan Toyo Europe) Remainder: Basecoat material with 19% solids content (acrylate-melamine) and diluent mixture. Example 13: Plastic 1 kg of polystyrene granules are wetted uniformly in a tumble mixer with 5 g bf adhesive. Then 42 g of granules from Example 6 are added and the components are mixed for 2 minutes. These granules are processed under standard conditions in an injection moulding machine to give small stepped plates measuring 4 X-3.X 0.5 cm. The stepped plates are notable for their lustre. Example 14 (comparative) Comparison of the dissolution rates of dried granules with granules containing approximately 4% by weight of solvent in a gravure printing ink. Example 15: 15.1 Preparation of the granulating solution 260.0 g of DI water at 50°C are introduced as an initial charge and 72 g of Rokramar 2150 granulat- ing resin (modified rosin from Kramer) are incor- porated by means of a 4-paddle stirrer. Then 17 g of 25% ammonia solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 (from Merck KGaA) are added with stirring, followed by stirring for 5 minutes. 15.2 Preparation of the granules 607 g of Iriodin® 305 Solargold (multilayer pigment based on mica with TiO2/Fe2O3 and SiO2 layers, of partiele size 10-60 µm from Merck KGaA) are placed in the mixer vessel and 393 g of granulating solution from Example 15.1 are slowly added. The mixture is mixed homo- geneously. The wetted mixture is granulated on a TR .01 granulating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated form their coarse fraction by passing them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The product is drive-resistant [sic] and dimen- sionally stable and is compatible, for example, with the customary solvent-free free-radically UV-curing Rayoflex extender varnish, 11 HF 60 (UV varnish) from Hartmann Druckfarben and with the solvent-containing extender varnish Haptobond CT 105 (based on nitrocellulose with ethanol as solvent) from Hartmann Druckfarben. The granules thus prepared also exhibit a high dissolution rate when incorporated by stirring into the said printing ink systems. Example 16: 16.1 Preparation of the granulating solution 256.4 g of DI water at 50°C are introduced as an initial charge and 66 g of Morez 300 granulating resin (polyacrylate resin from Morton) are incor- porated by means of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-2-methyl-l-propanol solution are added slowly and the mixture is stirred until the granulating resin has fully dissolved. Thereafter, 44 g of polyethylene glycol 1000 are added to the granulating solution with stirring, followed by stirring at 300 rpm for 5 minutes. 16.2 Preparation of the granules 597 g of Iriodin® 305 Solargold are placed in the mixer vessel and 403 g of granulating solution are slowly added. The mixture is mixed homogeneously. The wetted mixture is granulated on a TR 01 granu- lating plate from Eirich. The moist, granulated mixture is dried in a fluidized-bed dryer at from 80 to 120°C for 0.5-4 h, without going below a residual moisture content of 3% by weight. The granules thus prepared are first of all separated form their coarse fraction by passing, them through a sieve of mesh size 2 mm and then from their fine fraction by classifying using a 400 mm sieve. The granules obtained are abrasion-resistant, dimensionally stable, compatible and also readily soluble in the aqueous offset overprint varnish 350081 from Weilburger Lackfabrik. Sources: Merck KGaA International Lacquers S.A. Preparation: Introduce the nail varnish base and add the pigment granules with stirring. Leave to swell for 30 minutes and then stir at 1 000 rpm for 10 minutes. With the preparation method described, the granules can be incorporated without problems. Example 18: Shower gel with pigment preparation in granule form for water-based applications Preparation; For phase A, incorporate the pigment granules into the water with stirring. Incorporation is unproblematic and the granules dissolved immediately on addition of water. Scatter in Keltrol T slowly, with stirring, and stir until it has dissolved. Add phases B and C in succession, with slow stirring until all of the components are homogeneously distributed. Adjust pH to 6.0-6.5. Sources: (1) Merck KGaA (2) Kelco (3) Cognis GmbH (4) Haarmann & Reimer GmbH We Claim: 1. The process for the preparation of pigment in granule form comprising a resin or resin mixture, one or more effect pigments and, where appropriate, additives, wherein that the granules comprise 3-10% by weight of water or a solvent or solvent mixture having a vapor pressure of 0.001-40 hPas(20°C), wherein that the resin is an aldehyde or ketone resin, modified rosin, cellulose, cellulose derivative, sulfo polyester, polyacrylate resin, polymethacrylate resin or styrene-modified polyacrylate resin and the effect pigments are pearl luster pigments, metallic effect pigments, multiplayer pigments with transparent, or transparent and opaque, layers, holographic pigments, BIOCI or LCP (Liquid Crystal Polymer) pigments further the granules contain 0.05-10% by weight of a neutralizing agent, based on the granules. 2. The process as claimed in claim 1, wherein that the solvent is water, polyalkylene glycol, glycol ethers, diols, aliphatic triols having from 2 to 6 carbon atoms, glycerol 1, 2, 4-butanetriol, 1, 2, 6-hexanetriol or a mixture of two or three of the said solvents. 3. The process as claimed in claim 1 or 2, wherein that the granules contain - ? 4.5 - 30% by weight of resin or resin mixture and - ? 60% by weight of effect pigment, based on the granules. 4. The process as claimed in one of claims 1 to 3, wherein that the resin or resin mixture has an acid number of 90-350. 5. The process as claimed in claim 1, wherein that the pearl luster pigments are based on mica, SiO2, glass, TiO2 or Al2O3 platelets. 6. The process as claimed in claim 1 or 5, wherein that the pearl luster pigment is a mica, A12O3 or SiO2 platelet coated with TiO2, Fe2O3 or TiO2/Fe2O3. 7. The process as claimed in claim 1, wherein that the multiplayer pigment is a mica platelet coated with TiO2-SiO2-TiO2. 8. The process as claimed in one of claims 1 to 7, wherein that the granules further contain 0.05-10% by weight of a modifier, based on the granules. 9. The process as claimed in one of claims 1 to 11, wherein that the granules comprise an additional components defoamers, surface- active substances, wetting agents, anti-settling agents, levelling agents, siccatives and/or thixotropic agents. 10. The process as claimed in claim 1, wherein said granules are used in formulations such as paints, varnishes, powder, coating materials, printing inks, security printing inks, in plastics and in cosmetics. Pigment preparation in granule form comprising a resin or resin mixture, one or more effect pigments and, where appropriate, additives, wherein that the granules comprise 3-10 % by weight of water or a solvent or solvent mixture having a vapour pressure of 0.001-40 hPa (20ºC).

Full Text

(Pigment preparation in granule form)
The invention relates to pigment preparations in
granule form comprising one or more resins, one or more
effect pigments and, where appropriate, additives, the
granules being notable for comprising 3-10% by weight
of water or a solvent or solvent mixture having a
vapour pressure at 20°C of from 0.001 to 40 hPa.
In industrial processes, pigments are often not
employed in the form of dry powders, since such powders
produce dust, which leads to heightened requirements in
terms of workplace safety. In many cases, furthermore,
when introducing powders into plastics, basecoat
systems, etc., agglomeration of the pigment powder is
observed. Homogeneous distribution of the pigment in
the respective matrix is frequently difficult if not
impossible to achieve. In order to obtain the lustre
effect typical of pearl lustre pigments in a
formulation, extremely uniform distribution and
orientation of the pearl lustre pigment particles in
the binder is a necessity.
In applications, pigment granules feature a markedly
reduced dust nuisance and better free-flow properties
than pulverulent pigment preparations, and are
therefore garnering increasing interest. The additional
treatment of the pigments with a resin greatly enhances
the performance properties of the pigments.
EP 0 134 676 B1 discloses a process for preparing non-
dusting metal pigment compositions, in which the paste
is prepared by mixing an organic binder medium and a
metal pigment with an organic liquid vehicle. After the
end of the preparation process, the organic liquid
vehicle is removed from the coherent paste and the
resulting solid mass is divided into particles.
Solvent-free, free-flowing granules comprising pearl
lustre pigments and a binder and also additives, where
appropriate, are claimed, furthermore, in
EP 0 803 552 B1. The granules described therein are
especially suitable as precursors for printing inks.
The prior art granules which have been largely freed
from solvent during the preparation process, however,
are comparatively difficult to dissolve again in the
printing ink, and/or give rise to difficulties on
dispersing. For the homogenization of the pearl lustre
pigments from the granules in the formulation that is
to be prepared, mechanical forces are required, which
may in turn disrupt the platelets of the pearl lustre
pigments, thereby adversely affecting the optical
properties of the pigments.
It is an object of the present invention to provide
effect pigment formulations in the form of solid
particle forms which do not have the abovementioned
disadvantages and which possess a markedly higher
dissolution rate in binder systems than granules which
have been largely freed from solvent.
It has surprisingly been found that the dissolution
rate of granules comprising resins and effect pigments,
such as pearl lustre pigments, for example, resins and,
where appropriate, additives in printing inks or
coating materials can be significantly increased if the
granules are not freed completely from the solvent but
instead still contain a precisely defined amount of
solvent.
The invention accordingly provides pigment formulations
in solid particle form comprising effect pigments,
resins and, where appropriate, additives, characterized
in that they contain 3-10% by weight, based on the
granules, of a solvent which is non-volatile at room
temperature: The chosen solvent or solvent mixture is
selected so that it has a vapour pressure at 20°C of
from 0.001 to 40 hPa.
The granules of the invention are notable for an
increased dissolution rate when incorporated by
stirring into a binder system. Consequently, subsequent
homogenization of the formulation that is to be
prepared is made easier, since lower mechanical forces
are needed to dissolve the granules. The introduction
of foam into aqueous binder systems, and the risk of
fracture of particularly coarse pigment fractions, are
considerably reduced. Below the abovementioned solvent
content ( the solvation or solubility of the granules, especially
in solvent-containing and radiation-curing extenders,
is greatly reduced. Moreover, the precise metering of
the solvent content in the granules leads to better
wetting of the pigment particles.
The granules of the invention are non-dusting, free-
flowing, are much quicker to incorporate into
commercially available binder systems than the prior
art granules, and are compatible in the said systems.
In particular the products are compatible with aqueous,
solvent-containing and solvent-free printing ink and
coating systems. The inks and coating materials
prepared using the granules are suitable for gravure
printing, flexographic printing, screen printing,
offset overprint varnish (OPV) and also for the various
coating systems in the industrial coating and
automotive coating sectors. They are also suitable for
colouring plastics.
The pigment granules of the invention contain ? 60% by
weight, preferably 70-90% by weight, in particular 80-
90% by weight, of effect pigments. Very particular
preference is given to pigment preparations having an
effect pigment content of more than 80% by weight. The
percentages by weight are always based on the granules.
The effect pigments referred to here are pearl lustre
pigments, metallic effect pigments, multilayer pigments
with transparent and opaque layers, holographic
pigments, BiOCl and LCP (liquid crystal polymer)
pigments.
Particular preference is given to granules comprising
pearl lustre pigments based on platelet-shaped,
transparent or semi-transparent substrates. Examples of
suitable substrates are phyllosilicates, such as
natural or synthetic mica or other silicatic materials,
talc, sericite, kaolin and SiO2, glass, TiO2, graphite
and AL2O3 platelets. Examples of the platelet-shaped
substrates are those coated with rare earth metal
sulfides, such as Ce2S3, titanium suboxides, titanium
oxynitrides, pseudobrookite, with coloured or
colourless metal oxides, such as TiO2, (rutile or
anatase) Fe2O3, Fe3O4, SnO2, ZrO2, SiO2, Al2O3, Cr2O3, ZnO,
CuO, NiO, Ce2O3 and other metal oxides, alone or in a
mixture, in one uniform layer or in successive layers
(multilayer pigments). Pearl lustre pigments are known,
for example, from German patents and Patent
Applications 14 67 468, 19 59 998, 20 09 566,
22 14 454, 22 15 191, 22 44 298, 23 13 331, 25 22 572,
31 37 808, 31 37 809, 31 51 343, 31 51 354, 31 51 355,
32 11 602, 32 35 017 and P 38 42 330 and are available
commercially, e.g. under the brand name Iriodin® from
Merck KGaA, Darmstadt, Germany. Multilayer pigments
based on mica are sold, for example, by Merck KGaA or
by EM Industries under the brand name Timiron® Splendid
Copper, Timiron® Splendid Gold, Timiron® Splendid
Green, Iriodin® Solargold or Dichrona® Splendid.
Particularly preferred are multilayer pigments based on
mica having a TiO2-SiO2-TiO2 layer sequence.
Particularly preferred pigment granules comprise TiO2-,
Fe2O3- or TiO2/Fe2O3-coated mica, Al2O3 or SiO2 platelets.
The SiO2 platelets may be coated, for example, as
described in WO 93/08237 (wet-chemical coating) or
DE-A 196 14 637 (CVD process) . Al2O3 platelets are
known, for example, from EP 0 763 573 A1. Platelet-
shaped substrates coated with one or more rare earth
metal sulfides are disclosed, for example, in
DE-A 198 10 317.
Also suitable are metallic effect pigments, especially
aluminium flakes modified for aqueous and solvent-
containing systems, as sold by Eckart under the brand
name Rotovario Aqua or Stapa Hydroxal® for aqueous
applications, and also Variocrom® and Paliocrom®
pigments from BASF, including in particular those from
the Laid-Open Specifications EP 0 681 009 A1,
EP 0 632 110 A1, EP 0 634 458 A1, and also LCP pigments
(liquid crystal polymers). Examples of suitable effect
pigments from BASF are Variocrom ED 1478, Variocrom ED
1479 and Variocrom ED 1480. Likewise suitable,
furthermore, are all holographic pigments known to the
person skilled in the art, and also platelet-shaped
pigments which have metal layers. Pigments of this kind
are sold, among others, by Flex, for example, under the
brand names Chromaflair Red/Gold 000, Chromaflair
Gold/Silver 080, Chromaflair Green/Purple 190 and
Chromaflair Silver/Green 060. The Chromaflair pigments
with a particle size of about 11-13 µm consist of an
opaque aluminium core and a magnesium fluoride layer of
varying thickness which generates the later
interference colour of the resulting pigment.
Additionally, a semi-translucent chromium layer is
applied as the outermost layer.
The pigment granules of the invention may comprise one
or more effect pigments. In many cases it is possible
by using at least two different effect pigments to
obtain special colour effects and lustre effects.
Preferred pigment granules comprise one or two, or else
three, effect pigments, especially those pigments which
are based on mica and/or SiO2 platelets. Also possible
are blends of the effect pigments with organic and
inorganic pigments at up to 10% by weight based on the
granules, in which case the total amount of pigment
ought not to exceed 90% by weight, based on the
granules. Blending allows colour flops to be set in a
very targeted way. In particular, the addition of one
or more dyes and/or organic pigments in dispersed form
leads to special colour effects. It is also possible to
add those substances and particles (tracers) which
enable the product to be identified.
As a mandatory component, the granules of the invention
contain a resin or resin mixture in amounts of 4.5-30%
by weight, preferably 4.5-25% by weight, in particular
4.5-20% by weight, based on the pigment granules. The
acid number of the resin or resin mixture used is
preferably from 90 to 350, in particular from 120 to
280 and, with very particular preference, from 150 to
270.
Suitable resins include all natural, semi-synthetic and
fully synthetic resins or resin mixtures which are
known to the person skilled in the art and in which
effect pigments are commonly used. In particular,
mention may be made here of ketone resins, aldehyde
resins, cellulose and cellulose derivatives, such as
alkylcellulose, hydroxycelluloser hydroxyalkylcellu-
lose, cellulose acetobutyrate, cellulose nitrate,
rosins, polyacrylate or polymethacrylate resins, alkyd
resins, polyester resins, polyphenol resins, melamine
resins, polyterpene, polyvinyl, polyvinyl chloride and
polyvinylpyrrolidone resins, polystyrenes, polyolefins,
epoxy resins, polyurethanes, urea, aromatic-
formaldehyde resins, carbamic acid, sulfonamide and
sulfo polyesters.
Particularly good dispersibility and redispersibility
of the granules of the invention has been found if the
resins used comprise modified rosins, especially
styrene- and/or maleic-modified rosins, ketone and
aldehyde resins, cellulose and/or cellulose
derivatives, sulfo polyesters, styrene-modified
maleates, polyacrylate resins or polyraethacrylate
resins, and styrene-modified polyacrylate resins.
Particular preference is given to rosins which carry
carboxyl groups, such as maleic- and fumaric-acid-
modified rosins. Modified rosins are widely available
on the market and are sold, for example, by Kraemer
under the brand name Erkamar. Preference is also given
to styrene-modified polyacrylate resins, sold for
example under the brand name Morez by Morton.
A key constituent of the granules of the invention is
the solvent or - solvent mixture, which is present in
amounts of ? 3% by weight, but at most up to 10% by
weight, in the granules of the invention. The granules
preferably contain 3-7.5% by weight, especially 3-5.0%
by weight, of solvent, based on the granules. The
solvent component in the granules must in each case be
properly adapted to the resin system used. For
preparation it is possible to use water and also all
non-volatile organic solvents. Examples of suitable
solvents are aromatic solvents, e.g. toluenes,
petroleum spirits, xylenes, mineral oils, vegetable
oils, glycol ethers, such as propylene glycol monoethyl
ether, propylene glycol monoethyl ether or diols, such
as ethylene glycol and propylene glycol or polyether
diols, aliphatic triols and tetraols having from 2 to 6
carbon atoms, such as trimethylolethane, trimethylol-
propane, glycerol, 1,2,4-butanetriol and 1,2,6-
hexanetriol, alcohols, ketones, esters, and all other
solvents from other classes of compound, or a mixture
of two or three of the aforementioned solvents.
Particular preference is given to solvents having a
boiling point > 35°C, especially > 70°C. It is
preferred to use those solvents which are of medium or
high viscosity. Particular preference is given to
solvents which are readily miscible with water. It is
important that during the preparation the solvent
component includes at least one solvent or solvent
mixture which has a vapour pressure at 20°C of from
0.001 to 40 hPa, preferably from 0.001 to 30 hPa.
Particularly preferred solvents are water, polyalkylene
glycol, glycol ethers, diols, aliphatic triols having
2-6 carbon atoms, glycerol, 1,2,4-butanetriol, 1,2,6-
hexanetriol or a mixture of two or three of the
aforementioned solvents. The vapour pressures of the
suitable solvents may easily be determined by the
person skilled in the art or looked up in the Handbook
of Chemistry and Physics, 71st Edition, 1990-1991,
David R. Lide, CRC Press, chapter 6-48.
Particular preference is given to polyalkylene glycols,
toluene (29 hPa), xylene (10 hPa), 1,2-ethanediol
(0.053 hPa), 1,2,3-hexanetriol (0.01 hPa), 1,2,3-
propanetriol (0.001 hPa), and water (23 hPa). The water
may also contain dissolved sorbitol or urea. Preferred
polyalkylene glycols are polyethylene glycol (0.1 hPa)
and ethylene glycol monobutyl ether (0.8 hPa) (vapour
pressures at 20°C indicated in brackets in each case
are from, the Handbook of Chemistry and Physics).
As a further component, the granules preferably
comprise one or more neutralizing agents. Particularly
suitable agents are the bases: common in the coatings
sector, such as urea, urea derivatives, ammonia, amino
alcohols, such as 2-amino-2-methyl-l-propanol, alkali
metal hydroxides, such as KOH or NaOH, amines, the
latter in the case of granules for aqueous applications
preferably being organic amines of low molecular mass
which are non-volatile or possess a low volatility at
room temperature.
In general, the pigment granules of the invention
contain from 0-05 to 10% by weight of neutralizing
agent, preferably from 1 to 7% by weight, in particular
from 1.5 to 5% by weight, based on the pigment
granules.
The granules of the invention may further comprise a
modifier, as a further component, in amounts of from
0.05 to 10% by weight, preferably from 0.05 to 6% by
weight, in particular from 0.05 to 3% by weight. The
modifier used is in particular a polyalkylene oxide or
polyalkylene oxide derivative, whose purpose is to
enhance the strength of the granules and also their
compatibility.
If necessary, the addition of a redispersing agent in
the form of bulky particles, such as fibres or
spherical particles, for example, prevents the effect
pigments treated in accordance with the process of the
invention from lying on top. of one another to a notable
extent as a result of steric repulsion and so exerting
strong adhesion. The effect of this is that the
granules of the invention are more stable and the
effect pigments, after the granules have been
introduced into the paint, printing ink or coating
system, settle more slowly - in some cases very much
more slowly - and the sediment is in any case less
hard, and that no problems occur when the sediment is
reagitated.
The redispersing agent is used preferably in amounts of
from 0 to 5% by weight, in particular from 0.05 to 3%
by weight, based on the granules. All organic and
inorganic fibres having a fibre length of 0.1-20 µm
that are known to the person skilled in the art may be
used. Suitable particles are, in particular, all
synthetic fibres, e.g. those of polyethylene,
polyacrylates, polypropylene, polyamides, cellulose
fibres, inorganic fibres, including preferably silicon
compounds, glass fibres and also, in particular, the
condensation products of modified isocyanates and mono-
and diamines. These condensation products, comprising
diurea derivatives and also amino ureas containing
urethane groups, are known as thixotropic agents and
together with a binder are added to paints and coating
materials in order to improve the running properties
and the brushability.
As redispersing agents it is also possible to use all
diurea derivatives and urethane compounds that are
known to the person skilled in the art, as are
described, for example, in EP 0 198 519 and in Organic
Coatings: Science and Technology, A.. Heenriga, P.J.G.
von Hemsbergen, pp. 201-222, New York 1983.
Particularly - suitable spherical materials are hollow
glass, wax or polymer beads made of vinyl resins,
nylon, silicone, epoxy resins, olefin resins,
polystyrenes, and inorganic materials, such as TiO2,
SiO2 or ZrO2, for example. It is preferred to use hollow
beads, but also solid beads, having a particle size of
from 0.05 to 150 Mm. In the granules of the invention
it is particularly preferred to use hollow glass, wax
or polymer beads.
Spherical particles based on SiO2 in a particle range
of 3-10 µm are known, for example, as materials for
high-performance liquid chromatography and are sold,
for example, as LiChrospher® by Merck KGaA, Darmstadt,
FRG. Such materials are preferably used in monodisperse
form; that is, with a substantially uniform particle
size. Monodisperse spherical particles of this type
based on SiO2, TiO2 and ZrO2 are known. Monodisperse
SiO2, for example, may be prepared in accordance with
EP 0 216 278 B1. Hollow glass beads are sold, for
example, under the trade name Q-CEL by PQ Corporation,
USA, or Scotchlite by 3M, Frankfurt, FRG.
Additionally, the granules of the invention may
comprise surface-active substances, such as
alkylsilanes, for example, which may also contain a
further functional group, or saturated or unsaturated
fatty acids or fluorosurfactants. Particular preference
is given to using silane compounds of the formula
(CnH2n+1)Si(OCmH2m+1)3, where n is 1-30 and m is 1-10, as
surface-active substances. Examples of suitable silane
compounds are n-hexyldecyltriethoxysilane and n-octyl-
decyltriethoxysilane {Si 116 and Si 118 from Degussa
AG, Frankfurt) and also the corresponding fluoroalkyl-
silanes.
As surface-active substances it is also possible to use
the saturated and unsaturated fatty acids, such as
caproic acid, caprylic acid, capric acid, lauric acid,
myristic acid, palmitic acid, stearic acid, oleic acid
and linoleic acid, for example, and also fatty acid
mixtures.
The surface-active reagent may also comprise a mixture
of silane, fatty acids and/or surfactants. The granules
may contain from 0.1 to 5% by weight, preferably from
0.2 to 3% by weight and in particular from 0.5 to 2% by
weight of surface-active substances, based on the
pigment.
For the preparation of the granules, the pigments, the
resin and/or the resin mixture, and also the additives,
where present, are mixed with the solvent. The fraction
of the solvent at the beginning of the preparation is
between 20-40% by weight, preferably between 25-35% by
weight. During the preparation of the granules the
resin and/or resin mixture and also optionally further
additives are preferably premixed with the solvent
before being added to the pigment. This produces
intensive contact between pigment and the substances
required for the granulation, which at the same time
ensures more uniform covering of the pigment surface.
Subsequently, this mixture is gently homogenized.
Preferably, the pigment is introduced as the initial
charge and is first pasted up, with stirring, with the
solvent containing the resin and, if desired at this
stage, the modifier; subsequently, a further solution
consisting of solvent and additives is added.
During or after its production, further customary
additives may be added to this pigment preparation,
examples being defoamers, wetting agents, anti-settling
agents, levelling agents, emulsifiers, siccatives or
thixotropic agents. These are auxiliaries which are
customary in the coatings industry and may be present
in the granules of the invention in an amount of from 0
to 10% by weight. Mention is made here in particular of
succinate derivatives, examples being those as sold by
Henkel under the brand name Hydropalat 875.
To prepare the granules, the moist pigment preparation
is extruded or compacted into a compact particle form
by other methods known to the person skilled in the
art, such as by tableting, briquetting, pelletizing,
granulating, spray-granulating or fluidized-bed
granulating, and then dried under precisely controlled
conditions. In the course of the drying operation, the
solvent content of the granules is measured
continuously. Depending on the solvent used, the drying
process . takes place at temperatures of from 60 to
150°C, preferably at from 60 to 120°C, and may where
appropriate take place under reduced pressure,
preferably at 80-100 mbar. The duration of drying
depends on the batch size of the preparation to be
dried, its throughput in the course of drying, and the
solvent used, but is generally 0.5-24 h, preferably
1-18 h. As soon as the granules have a residual solvent
moisture content of ? 3% by weight, but = 10% by
weight, the drying operation is halted. Finally, the
granules are classified where necessary.
The term "granules" as used herein embraces all
possible solid particle forms, such as pellets, chips,
briquettes, tablets, etc. The particle sizes of the
granules are situated within the range from 0.1 to
150 mm, preferably from 0.1 to 20 mm, in particular
from 0.1 to 6 mm.
The determination of the residual solvent moisture
content in the course of the preparation process takes
place using a Sartorius MA 30 moisture analyzer, which
works on an infrared basis. Following calibration, the
water content is measured. Where further solubility
enhancers are to be measured, this is done in
accordance with the principle of differential weighing,
since the substances to be analysed may be expelled
together with the water above the previously calibrated
temperature. There remains only the fraction of
polymeric substance/resin and the effect pigment.
When measuring the water content using the Sartorious
MA 30 moisture analyzer, the following parameters may
be chosen in order to find the result:
Initial sample mass: 4-5 g of unground substance-
Temperature: 135-160°C
Time setting: 12-20 minutes
Result indication: 0-100% (solvent content).
The granules of the invention may be used for diverse
applications. They are preferably used in coating
systems from the sectors of printing, especially
overprint varnishing, offset overprint varnishing,
gravure, flexographic and screen printing. With
particular preference, the granules as precursors for
coating materials are applied to any desired substrate
materials, examples being metals such as iron, steel,
aluminium, copper, bronze, plastic, brass and also
metal foils, and also glass, ceramic and concrete, and
also wood, e.g. furniture, clay, textile, paper,
packaging materials, e.g. plastic containers, films or
boards, or to other materials for decorative and/or
protective purposes. Furthermore, the granules of the
invention are suitable in formulations for producing
security features.
Accordingly, the invention also provides for the use of
the granules of the invention in formulations such as
paints, printing inks, security printing inks, coating
materials, powder coating materials, coatings such as
industrial and automotive coatings, in plastics, and in
cosmetics.
The examples which follow are intended to illustrate
the invention without, however, restricting it.
Examples
Example 1
1.1 Preparation of the granulating solution
260.0 g of DI water at 50°C are introduced as an
initial charge and 72 g of Rokramar 2150
granulating resin (modified rosin from Kramer) are
incorporated by means of a 4-paddle stirrer. Then
17 g of 25% ammonia solxttion are added slowly and
the mixture is stirred until the granulating resin
has fully dissolved. Thereafter, 44 g of
polyethylene glycol 1000 (from Merck KGaA) are
added with stirring, followed by stirring for
5 minutes.
1.2 Preparation of the granules
To prepare the granules, thorough mixing must be
ensured. On the 1 kg scale, the mixture is
prepared with the aid of an Eirich R02 mixer.
607 g of Iriodin® 231 (TiO2/mica pigment of
particle size 5-25 urn from Merck KGaA, Germany)
are placed in the mixer vessel and 393 g of
granulating solution from Example 1.1.are slowly
added. The mixture is mixed homogeneously. The
wetted mixture is granulated on a TR 01
granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all separated from their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 µm sieve. The solvent content of the
granules in the drying process is measured
continuously using the Sartorius MA 30 moisture
analyzer. The following parameters were chosen in
order to find the result:
Initial sample mass: 4-5 g of unground substance
Temperature: 160°C
Time setting: 20 minutes
Result indication: 0-100% (solvent content).
The product is abrasion-resistant and
dimensionally stable and is compatible, for
example, with the customary solvent-free, free-
radically UV-curing Rayoflex extender varnish,
11 HF 60 (UV varnish) from Hartmann Druckfarben
and with the solvent-containing extender varnish
Haptobond CT 105 (based on nitrocellulose with
ethanol as solvent) from Hartmann Druckfarben. The
granules thus prepared also exhibit a high
dissolution rate when incorporated by stirring
into the said printing ink systems.
Example 2
2.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as an
initial charge and 66 g of Morez 300 granulating
resin (polyacrylate resin from Morton) are
incorporated by means of a 4-paddle stirrer. Then
36.6 g of 75% 2-amino-2-methyl-1-propanol solution
are added slowly and the mixture is stirred until
the granulating resin has fully dissolved.
Thereafter, 44 g of polyethylene glycol 1000 are
added with stirring, followed by stirring at 300
rpm for 5 minutes.
2.2 Preparation of the granules
597 g of Iriodin® 231 (TiO2/mica pigment of
particle size 5-25 mm from Merck KgaA) are placed
in the mixer vessel and 403 g of granulating
solution are slowly added. The mixture is mixed
homogeneously. The wetted mixture is granulated on
a TR 01 granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all. separated from their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 µm sieve. The solvent content of the
granules in the drying process is measured
continuously using the Sartorius MA 30 moisture
analyzer. The following parameters were chosen in
order to find the result:
Initial sample mass: 4-5 g of unground substance
Temperature: 135°C
Time setting: 12 minutes
Result indication: 0-100% (solvent content).
The granules obtained possess a residual moisture
content of approximately 4 ± 0.5% by weight and
are abrasion-resistant, dimensionally stable,
compatible, and also readily soluble in the
aqueous offset overprint varnish 350081 from
Weilburger Lackfabrik.
Example 3
3.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as an
initial charge and 66 g of Morez 300 granulating
resin are incorporated by means of a 4-paddle
stirrer. Then 36.6 g of 75% 2-amino-2-methyl-l-
propanol solution are added slowly and the mixture
is stirred until the granulating resin has fully
dissolved. Thereafter, 44 g of polyethylene glycol
1000 are added with stirring, followed by stirring
at 300 rpm for 5 minutes.
3.2 Preparation of the granules
597 g of Iriodin® 103 (TiO2/mica pigment of
particle size 10-60 mm, Merck KGaA, Darmstadt,
Germany) are introduced and 403 g of granulating
solution are slowly added. At a speed of 300-
500 rpm, 19.5 g of Solcolor Green (CI PG 7)
pigment preparation from MK Chemicals are added as
well. The mixture is mixed homogeneously. The
wetted mixture is granulated on a TR 01
granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. This gives greenish pearl lustre granules
having interesting colouristic properties. The
granules thus prepared are first of all separated
from their coarse fraction by passing them through
a sieve of mesh size 2 mm and then from their fine
fraction by classifying using a 400 mm sieve.
The product possesses a residual moisture content
of 4 ± 0.5% by weight and is abrasion-resistant,
dimensionally stable, compatible, and also readily
soluble in the common offset overprint varnish
350081 from Weilburger Lackfabrik.
Example 4
4.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as an
initial charge and 66 g of Morez 300 granulating
resin are incorporated by means of a 4-paddle
stirrer. Then 36.6 g of 75% 2-amino-2-methyl-1-
propanol solution are added slowly and the mixture
is stirred until the granulating resin has fully
dissolved. Thereafter, 44 g of polyethylene glycol
1000 are added with stirring, followed by stirring
at 300 rpm for 5 minutes.
4.2 Preparation of the granules
597. g of Iriodin® 103 are placed in the mixer
vessel and 403 g of granulating solution are
slowly added. At a speed of 300-500 rpm, 19.5 g of
Solcolor Yellow (CI PY 83) pigment preparation
from MK Chemicals are added as well. The mixture
is mixed homogeneously.
The wetted mixture is granulated on a TR 01
granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. This gives yellowish pearl lustre granules
having interesting colouristic properties. The
granules thus prepared are first of all separated
from their coarse fraction by passing them through
a sieve of mesh size 2 mm and then from their fine
fraction by classifying using a 400 mm sieve.
The granules possess a residual moisture content
of 4 ± 1% by weight and are abrasion-resistant,
dimensionally stable, compatible, and also readily
soluble in the common aqueous offset overprint
varnish 350081 from Weilburger Lackfabrik.
Example 5
5.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as an
initial charge and 66 g of Morez 300 granulating
resin (polyacrylate resin from Morton) are
incorporated by means of a 4-paddle stirrer. Then
36.6 g of 75% 2-amino-2-methyl-l-propanol solution
are added slowly and the mixture is stirred until
the granulating resin has fully dissolved.
Thereafter, 44 g of polyethylene glycol 1000 are
added with stirring, followed by stirring at
300 rpm for 5 minutes.
5.2 Preparation of the granules
To prepare the granules, thorough mixing must be
ensured. On the 1 kg scale, the mixture is
prepared with the aid of an Eirich R02 mixer.
597 g of Paliocrom® Gold L2002 from BASF AG are
placed in the mixer vessel and 403 g of
granulating solution are slowly added. The mixture
is mixed homogeneously. The wetted mixture is
granulated on a TR 01 granulating plate from
Eirich. The moist, granulated mixture is dried in
a fluidized-bed dryer at from 80 to 120°C for 0.5-
4 h, without going below a residual moisture
content of 3% by weight. The granules thus
prepared are first of all separated from their
coarse fraction by passing them through a sieve of
mesh size 2 mm and then from their fine fraction
by classifying using a 400 mm sieve.
The solvent content of the granules in the drying
process is measured continuously using the
Sartorius MA 30 moisture analyzer. The following
parameters were chosen in order to find the
result:
Initial sample mass: 4-5 g of unground substance
Temperature: 135°C
Time setting: 12 minutes
Result indication: 0-100% (solvent content)
The granules obtained possess a residual moisture
content of approximately 5 ± 0.5% by weight and
are abrasion-resistant, dimensionally stable,
compatible, and also readily soluble in the
aqueous offset overprint varnish 350081 from
Weilburger Lackfabrik.
Example 6
6.1 Preparation of the granulating solution
260.0 g of DI water at 50°C are introduced as an
initial charge and 72 g of Rokramar 2150
granulating resin (modified rosin from Kramer) are
incorporated by means of a paddle stirrer. Then
17 g of 25% ammonia solution are added slowly and
the mixture is stirred until the granulating resin
has fully dissolved. Thereafter, 44 g of
polyethylene glycol 1000 (from Merck KGaA) are
added with stirring, followed by stirring for
5 minutes.
6.2 Preparation of the granules
To prepare the granules, thorough mixing must be
ensured. On the 1 kg scale, the mixture is
prepared with the aid of an Eirich R02 mixer.
607 g of Colorstream® Autumn Mystery (Fe2O3-coated
SiO2 platelet of particle size 5-40 mm from Merck
KGaA, Germany) are placed in the mixer vessel and
393 g of granulating solution from Example 6.1 are
slowly added. The mixture is mixed homogeneously.
The wetted mixture is granulated on a TR 01
granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all separated from their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 mm sieve.
The product is abrasion-resistant and
dimensionally stable and is compatible, for
example, with the customary solvent-free, free-
radically UV-curing Rayoflex extender varnish,
11 HF 60 (UV varnish) from Hartmann Druckfarben
and with the solvent-icontaining extender varnish
Haptobond CT 105 (based on nitrocellulose with
ethanol as solvent) from Hartmann Druckfarben. The
granules thus prepared also exhibit a high
dissolution rate when incorporated by stirring
into the said printing ink systems.
Example 7
7.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as an
initial charge and 66 g of Morez 300 granulating
resin (polyacrylate resin from Morton) are
incorporated by means of a 4-paddle stirrer. Then
36.6 g of 75% 2-amino-2-methyl-1-propanol solution
are added slowly and the mixture is stirred until
the granulating resin has fully dissolved.
Thereafter, 44 g of polyethylene glycol 1000 are
added to the granulating solution with stirring,
followed by stirring at 300 rpm for 5 minutes.
7.2 Preparation of the granules
597 g of Chromaflair Silver/Green 060 effect
pigment from Flex (aluminium substrate with an
MgF2 layer and an outer Cr layer, of particle size
11-13 mm) are placed in the mixer vessel and 4.03 g
of granulating solution from Example 7.1 are
slowly added. The mixture is mixed homogeneously.
The wetted mixture is granulated on a TR 01
granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all separated from their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 mm sieve. The solvent content of the
granules in the drying process is measured
continuously using the Sartorius MA 30 moisture
analyzer. The following parameters were chosen in
order to find the result:
Initial sample mass: 4-5 g of unground substance
Temperature: 135°C
Time setting: 12 minutes
Result indication: 0-100% (solvent content).
The granules obtained possess a residual moisture
content of approximately 4 ± 0.5% by weight and
are abrasion-resistant, dimensionally stable,
compatible, and also readily soluble in the
aqueous offset overprint varnish 350081 from
Weilburger Lackfabrik.
Example 8
8.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as an
initial charge and 66 g of Morez 300 granulating
resin (polyacrylate resin from Morton) are
incorporated by means of a 4-paddle stirrer. Then
36.6 g of 75% 2-amino-2-methyl-1-propanol solution
tare added slowly and the mixture is stirred until
the. granulating resin has fully dissolved.
Thereafter, 44 g of polyethylene glycol 1000 are
added to the granulating solution with stirring,
followed by stirring at 300 rpm for 5 minutes.
8.2 Preparation of the granules
597 g of Variocrom ED 1478 from BASF AG are placed
in the mixer vessel and 403 g of granulating
solution are slowly added. The mixture is mixed
homogeneously. The wetted mixture is granulated on
a TR 01 granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all separated from their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 mm sieve.
The solvent content of the granules in the drying
process is measured continuously using the
Sartorius MA 30 moisture analyzer. The following
parameters were chosen in order to find the
result:
Initial sample mass: 4-5 g of unground substance
Temperature: 135°C
Time setting: 12 minutes.
Result indication: 0-100% (solvent content)
The granules obtained possess a residual moisture
content of approximately 4 ± 0.5% by weight and
are abrasion-resistant, dimensionally stable,
compatible, and also readily soluble in the
aqueous offset overprint varnish 350081 from
Weilburger Lackfabrik.
Example 9
9.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as. an
initial charge and 66 g of Morez 300 granulating
resin (polyacrylate resin from Morton) are
incorporated within 1 minute at 300 rpm by means
of a 4-paddle stirrer. Then 36.6 g of 75% 2-amino-
2-methyl-1-propanol solution are added slowly and
the mixture is stirred until the granulating resin
has fully dissolved. Thereafter, 44 g of
polyethylene glycol 1000 are added to the
granulating solution with stirring, followed by
stirring at 300 rpm for 5 minutes.
9.2 Preparation of the granules
597 g of 610 0 010 Non-Leafing Silver (acrylic
based) from Eckart (aluminium effect pigment of
particle size D50 = 8 mm) are placed in the mixer
vessel and 403 g of granulating solution are
slowly added. The mixture is mixed homogeneously.
The wetted mixture is granulated on a TR 01
granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all separated from their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 mm sieve.
The solvent content of the granules in the drying
process is measured continuously using the
Sartorius MA 30 moisture analyzer. The following
parameters were chosen in order to find the
result:
Initial sample mass: 4-5 g of unground substance
Temperature: 135°C
Time setting: 12 minutes
Result indication: 0-100% (solvent content).
The granules obtained possess a residual moisture
content of approximately 4 ± 0.5% by weight and
are abrasion-resistant, dimensionally stable,
compatible, and also readily soluble in the
aqueous offset overprint varnish 350081 from
Weilburger Lackfabrik.
Example 10
10.1 Preparation of the granulating solution
260.0 g of DI water at 50°C are introduced as an
initial charge and 72 g of Rokramar 2150
granulating resin (modified rosin from Kramer) are
incorporated by means of a 4-paddle stirrer. Then
17 g of 25% ammonia solution are added slowly and
the mixture is stirred until the granulating resin
has fully dissolved. Thereafter, 44 g of
polyethylene glycol 1000 (from Merck KGaA) are
added with stirring, followed by stirring for
5 minutes.
10.2 Preparation of the granules
607 g of Timiron® Splendid Gold from Merck KGaA or
EM Industries (multilayer pigment based on mica
with alternating SiO2 and TiO2 layers, of particle
size 10-60 mm) are placed in the mixer vessel and
393 g of granulating solution from Example 10.1
are slowly added. The mixture is mixed
homogeneously. The wetted mixture is granulated on
a TR 01 granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all separated from their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 mm sieve. The solvent content of the
granules in the drying process is measured
continuously using the Sartorius MA 30 moisture
analyzer. The following parameters were chosen in
order to find the result:
Initial sample mass: 4-5 g of unground substance
Temperature: 160°C
Time setting: 20 minutes
Result indication: 0-100% (solvent content)
The product is abrasion-resistant and
dimensionally stable and is compatible, for
example, with the customary solvent-free, free-
radically UV-curing Rayoflex extender varnish,
11 HF 60 (UV varnish) from Hartmann Druckfarben
and with the solvent-containing extender varnish
Haptobond CT 105 (based on nitrocellulose with
ethanol as solvent) from Hartmann Druckfarben. The
granules thus prepared also exhibit a high
dissolution rate when incorporated by stirring
into the said printing ink systems.
Example 11
11.1 Preparation of the granulating solution
231.1 g of Eastek 1300 (30% sulfo polyester
dispersion in water, pH = 6; density: 1.08 g/cm3;
MFT: 12°C) are introduced as an initial charge and
144.3 g of DI water are stirred in using a 4-
paddle stirrer. This solution is used as a
granulating solution to prepare effect pigment
granules.
11.2 Preparation of the granules
624.6 g of Iriodin® 231 from Merck KGaA are placed
in the mixing vessel and 375.4 g of granulating
solution from Example 11.1 are slowly added. The
mixture is mixed homogeneously. The wetted mixture
is granulated on a TR 01 granulating plate from
Eirich. The wet, granulated mixture is dried in a
fluidized-bed dryer at from 80 to 120°C for 0.5-
4 h, without going below a residual moisture
content of 3% by weight. The granules thus
prepared are first of all separated from their
coarse fraction by passing them through a sieve of
mesh size 2 mm and then from their fine fraction
by classification using a 400 mm sieve.
The granules obtained are abrasion-resistant,
dimensionally stable and compatible and also
readily soluble in the aqueous offset overprint
varnish 350081 from Weilburger Lackfabrik.
Example 12: Paint
Formulations consisting of
3.00% pigment granules from Example 1
1.50% Monastral green 6Y spec, (from Zeneca)
0.50% Cappoxyt yellow 4214 (from Cappelle)
0.03% FW 200 pigment black (from Degussa)
0.40% dollar aluminium Alpate 7620 NS (from Alcan Toyo
Europe)
Remainder: Basecoat material with 19% solids
content (acrylate-melamine) and diluent
mixture.
Example 13: Plastic
1 kg of polystyrene granules are wetted uniformly in a
tumble mixer with 5 g bf adhesive. Then 42 g of
granules from Example 6 are added and the components
are mixed for 2 minutes. These granules are processed
under standard conditions in an injection moulding
machine to give small stepped plates measuring
4 X-3.X 0.5 cm. The stepped plates are notable for
their lustre.
Example 14 (comparative)
Comparison of the dissolution rates of dried
granules with granules containing approximately 4%
by weight of solvent in a gravure printing ink.
Example 15:
15.1 Preparation of the granulating solution
260.0 g of DI water at 50°C are introduced as an
initial charge and 72 g of Rokramar 2150 granulat-
ing resin (modified rosin from Kramer) are incor-
porated by means of a 4-paddle stirrer. Then 17 g
of 25% ammonia solution are added slowly and the
mixture is stirred until the granulating resin has
fully dissolved. Thereafter, 44 g of polyethylene
glycol 1000 (from Merck KGaA) are added with
stirring, followed by stirring for 5 minutes.
15.2 Preparation of the granules
607 g of Iriodin® 305 Solargold (multilayer
pigment based on mica with TiO2/Fe2O3 and SiO2
layers, of partiele size 10-60 µm from
Merck KGaA) are placed in the mixer vessel and
393 g of granulating solution from Example 15.1
are slowly added. The mixture is mixed homo-
geneously. The wetted mixture is granulated on a
TR .01 granulating plate from Eirich. The moist,
granulated mixture is dried in a fluidized-bed
dryer at from 80 to 120°C for 0.5-4 h, without
going below a residual moisture content of 3% by
weight. The granules thus prepared are first of
all separated form their coarse fraction by
passing them through a sieve of mesh size 2 mm and
then from their fine fraction by classifying using
a 400 mm sieve.
The product is drive-resistant [sic] and dimen-
sionally stable and is compatible, for example,
with the customary solvent-free free-radically
UV-curing Rayoflex extender varnish, 11 HF 60 (UV
varnish) from Hartmann Druckfarben and with the
solvent-containing extender varnish Haptobond
CT 105 (based on nitrocellulose with ethanol as
solvent) from Hartmann Druckfarben. The granules
thus prepared also exhibit a high dissolution rate
when incorporated by stirring into the said
printing ink systems.
Example 16:
16.1 Preparation of the granulating solution
256.4 g of DI water at 50°C are introduced as an
initial charge and 66 g of Morez 300 granulating
resin (polyacrylate resin from Morton) are incor-
porated by means of a 4-paddle stirrer. Then
36.6 g of 75% 2-amino-2-methyl-l-propanol solution
are added slowly and the mixture is stirred until
the granulating resin has fully dissolved.
Thereafter, 44 g of polyethylene glycol 1000 are
added to the granulating solution with stirring,
followed by stirring at 300 rpm for 5 minutes.
16.2 Preparation of the granules
597 g of Iriodin® 305 Solargold are placed in the
mixer vessel and 403 g of granulating solution are
slowly added. The mixture is mixed homogeneously.
The wetted mixture is granulated on a TR 01 granu-
lating plate from Eirich. The moist, granulated
mixture is dried in a fluidized-bed dryer at from
80 to 120°C for 0.5-4 h, without going below a
residual moisture content of 3% by weight. The
granules thus prepared are first of all separated
form their coarse fraction by passing, them through
a sieve of mesh size 2 mm and then from their fine
fraction by classifying using a 400 mm sieve.
The granules obtained are abrasion-resistant,
dimensionally stable, compatible and also readily
soluble in the aqueous offset overprint varnish
350081 from Weilburger Lackfabrik.
Sources:
Merck KGaA
International Lacquers S.A.
Preparation:
Introduce the nail varnish base and add the pigment
granules with stirring. Leave to swell for 30 minutes
and then stir at 1 000 rpm for 10 minutes.
With the preparation method described, the granules can
be incorporated without problems.
Example 18: Shower gel with pigment preparation in
granule form for water-based applications
Preparation;
For phase A, incorporate the pigment granules into the
water with stirring. Incorporation is unproblematic and
the granules dissolved immediately on addition of
water. Scatter in Keltrol T slowly, with stirring, and
stir until it has dissolved. Add phases B and C in
succession, with slow stirring until all of the
components are homogeneously distributed. Adjust pH to
6.0-6.5.
Sources:
(1) Merck KGaA
(2) Kelco
(3) Cognis GmbH
(4) Haarmann & Reimer GmbH
We Claim:
1. The process for the preparation of pigment in granule form
comprising a resin or resin mixture, one or more effect pigments
and, where appropriate, additives, wherein that the granules
comprise 3-10% by weight of water or a solvent or solvent mixture
having a vapor pressure of 0.001-40 hPas(20°C), wherein that the
resin is an aldehyde or ketone resin, modified rosin, cellulose,
cellulose derivative, sulfo polyester, polyacrylate resin,
polymethacrylate resin or styrene-modified polyacrylate resin and
the effect pigments are pearl luster pigments, metallic effect
pigments, multiplayer pigments with transparent, or transparent
and opaque, layers, holographic pigments, BIOCI or LCP (Liquid
Crystal Polymer) pigments further the granules contain 0.05-10%
by weight of a neutralizing agent, based on the granules.
2. The process as claimed in claim 1, wherein that the solvent is
water, polyalkylene glycol, glycol ethers, diols, aliphatic triols
having from 2 to 6 carbon atoms, glycerol 1, 2, 4-butanetriol, 1, 2,
6-hexanetriol or a mixture of two or three of the said solvents.
3. The process as claimed in claim 1 or 2, wherein that the granules
contain
- ? 4.5 - 30% by weight of resin or resin mixture and
- ? 60% by weight of effect pigment,
based on the granules.
4. The process as claimed in one of claims 1 to 3, wherein that the
resin or resin mixture has an acid number of 90-350.
5. The process as claimed in claim 1, wherein that the pearl luster
pigments are based on mica, SiO2, glass, TiO2 or Al2O3 platelets.
6. The process as claimed in claim 1 or 5, wherein that the pearl
luster pigment is a mica, A12O3 or SiO2 platelet coated with TiO2,
Fe2O3 or TiO2/Fe2O3.
7. The process as claimed in claim 1, wherein that the multiplayer
pigment is a mica platelet coated with TiO2-SiO2-TiO2.
8. The process as claimed in one of claims 1 to 7, wherein that the
granules further contain 0.05-10% by weight of a modifier, based
on the granules.
9. The process as claimed in one of claims 1 to 11, wherein that the
granules comprise an additional components defoamers, surface-
active substances, wetting agents, anti-settling agents, levelling
agents, siccatives and/or thixotropic agents.
10. The process as claimed in claim 1, wherein said granules are used
in formulations such as paints, varnishes, powder, coating
materials, printing inks, security printing inks, in plastics and in
cosmetics.
Pigment preparation in granule form comprising a resin or resin
mixture, one or more effect pigments and, where appropriate,
additives, wherein that the granules comprise 3-10 % by weight of
water or a solvent or solvent mixture having a vapour pressure of
0.001-40 hPa (20ºC).

Documents:

403-KOLNP-2003-FORM-27.pdf

403-kolnp-2003-granted-abstract.pdf

403-kolnp-2003-granted-claims.pdf

403-kolnp-2003-granted-correspondence.pdf

403-kolnp-2003-granted-description (complete).pdf

403-kolnp-2003-granted-examination report.pdf

403-kolnp-2003-granted-form 1.pdf

403-kolnp-2003-granted-form 18.pdf

403-kolnp-2003-granted-form 2.pdf

403-kolnp-2003-granted-form 3.pdf

403-kolnp-2003-granted-form 5.pdf

403-kolnp-2003-granted-gpa.pdf

403-kolnp-2003-granted-letter patent.pdf

403-kolnp-2003-granted-others.pdf

403-kolnp-2003-granted-priority document.pdf

403-kolnp-2003-granted-reply to examination report.pdf

403-kolnp-2003-granted-specification.pdf

403-kolnp-2003-granted-translated copy of priority document.pdf

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Patent Number

214096

Indian Patent Application Number

403/KOLNP/2003

PG Journal Number

05/2008

Publication Date

01-Feb-2008

Grant Date

30-Jan-2008

Date of Filing

03-Apr-2003

Name of Patentee

MERCK PATENT GMBH.

Applicant Address

FRANKFURTER STRASSE 250, 64293 DARMSTADT

Inventors:

#	Inventor's Name	Inventor's Address
1	RATHSCHLAG, THOMAS	AUFDEM ROTLAUF 4, 35781 WEILBURG
2	SCHOEN, SABINE	GUNDOLFSTRASSE 25 , 64287 DARMSTADT

PCT International Classification Number

C09D 17/00

PCT International Application Number

PCT/EP01/10343

PCT International Filing date

2001-09-07

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	100 46 152.2	2000-09-15	Germany