DE102009030250A1 - Diffraction color pigment, useful e.g. in powder coatings, inks and toners, and in the production of masterbatches, comprises a portion of arrays of spherical cavities with a monodisperse size distribution for the optical properties - Google Patents

Abstract

Diffraction color pigment comprises a portion of arrays of spherical cavities with a substantially monodisperse size distribution for the optical properties. Independent claims are included for: (1) a preparation comprising at least one diffraction color pigment and at least one suitable carrier; (2) preparing a composition for topical application, comprising mixing at least a diffraction color pigment with at least one suitable carrier and optionally other ingredients; and (3) producing diffraction color pigment, comprising producing a three-dimensional packing of spheres, constructing the matrix around the sphere aggregates, removing the sphere aggregates and crushing the resulting shaped body to pigments.

Description

The The invention relates to pigments based on diffractive colorants, preparations containing such pigments and methods for producing the Pigments and preparations and their use.

in the Environment of decorative applications and the design of surfaces With a high perceived value there is a constant need for new ones Effect materials. Commercially available effect colorants are currently In addition to dyes, for example, interference pigments. Also the use of diffractive colorants with opal-like effects is recurring discussed.

such Diffractive colorants differ in stability and Processability, however, clearly from classic pigments. Therefore there is a need for diffractive colorant pigments to ask for stability and processability as little as possible of classical pigments, such as interference pigments differ.

One The first object of the present invention is therefore a diffractive colorant pigment, that in the essential for the optical properties Proportion essentially of arrangements of spherical cavities with a substantially monodisperse size distribution consists.

there the diffractive colorant pigments are preferably those in the form of platelets or spheres, preferably their thickness in the range of 0.5 to 20 .mu.m, particularly preferably in Range 1 to 10 microns. It is preferable in the diffractive colorant pigments of the invention platelet-shaped particles whose thickness is preferably in the range of 0.5 to 20 .mu.m, particularly preferably in Range 1 to 10 microns.

Diffractive colorants For the purposes of the present invention are materials that are three-dimensional have photonic structures. Under three-dimensional photonic Structures become i. a. Understood systems that have a regular, three-dimensional modulation of the dielectric constant (and thereby also the refractive index). Corresponds to the periodic modulation length in about the wavelength of the (visible) light, the structure follows with the light Kind of a three-dimensional diffraction grating interacting what expresses itself in angle-dependent color phenomena.

The inverse structure of the opal structure is conceived by arranging regular spherical hollow volumes in a dense packing in a solid material. An advantage of such inverse structures over the normal structures is the emergence of photonic bandgaps at already much lower dielectric constant contrasts ( K. Busch et al. Phys. Rev. Letters E, 198, 50, 3896 ).

Diffractive colorants The cavities must therefore have a fixed Own matrix. In a variant of the invention, the matrix exists essentially of an organic polymer, preferably is networked. In another variant of the invention, the matrix exists around the cavities essentially of an inorganic one Material, preferably a metal or metalloid or a metal chalcogenide or Metallpnictid consist, in particular Silciumdioxid, alumina, Zirconia, iron oxides, titanium dioxide, ceria, gallium nitride, boron and aluminum nitride and silicon and phosphonitride or mixtures of which are preferred. In particular, it is preferred if the matrix is composed of alumina, zirconia, titania, Ceria, or mixtures or mixed oxides thereof or mixtures or mixed oxides thereof with silica.

Especially it is preferred according to the invention, when the middle Diameter of the cavities in the range of about 50-500 nm, preferably in the range of 100-500 nm and especially preferably in the range of 200 to 280 nm.

• • Als Struktur gebende Template werden monodisperse Kugeln in einer dichtesten Kugelpackung angeordnet.
• • Die Hohlvolumina zwischen den Kugeln werden durch Ausnutzung von Kapillareffekten mit einem gasförmigen oder flüssigen Precursor oder einer Lösung eines Precursors befüllt.
• • Der Precursor wird (thermisch) in das gewünschte Material umgesetzt.
• • Die Template werden entfernt, wobei die inverse Struktur zurückbleibt.

Three-dimensional inverse structures ie diffractive colorants to be used according to the invention with regular arrangements of cavities can be produced, for example, by a template synthesis:

• • As structure-giving templates monodisperse spheres are arranged in a densest sphere packing.
• The hollow volumes between the balls are filled by utilizing capillary effects with a gaseous or liquid precursor or a solution of a precursor.
• • The precursor is converted (thermally) into the desired material.
• • The templates are removed, leaving behind the inverse structure.

By a subsequent milling step may be appropriate Diffraction colorant shaped body in the sense of the present invention Invention are crushed into pigments. This is done by cutting, Breaking and / or grinding into pigments of suitable size. This process can be done, for example, in a continuous belt process respectively. It can be used a rolling mill or a grinder. Are particularly uniform particle sizes When pigments are desired, so can Connect the comminution step one or more sieve steps.

One The present invention is therefore a method for Preparation of a diffractive colorant pigment, wherein in a first Step, a three-dimensional sphere package is generated, in a second Step the matrix is built around the ball aggregates and in a third party subsequent or simultaneous step removes the ball aggregates and in a fourth step, the resulting moldings be crushed into pigments.

Many different processes for preparing inverse diffraction colorant structures are described in the literature, which can be used as partial steps in the preparation of the pigments according to the invention: For example, SiO ₂ spheres can be arranged in a densest packing, the hollow volumes are filled with solutions containing tetraethyl orthotitanate. After several tempering steps, the balls are removed in an etching process with HF, leaving the inverse structure of titanium dioxide ( Colvin, et al. Adv. Mater. 2001, 13, 180 ).

De La Rue et al. ( De La Rue et al. Synth. Metals, 2001, 116, 469 ) describe the preparation of inverse, consisting of TiO ₂ opal according to the following method: A dispersion of 400 nm large polystyrene beads is dried on a filter paper under an IR lamp. The filter cake is aspirated with ethanol, transferred to a glovebox and infiltrated by means of a water jet pump with tetraethyl orthotitanate. Carefully remove the filter paper from the latex-ethoxide composite and transfer the composite to a tube furnace. In the tube furnace takes place at 575 ° C, the 8 h lasting calcination in an air flow, which is formed from the ethoxide titanium dioxide and the latex particles are burned out. An inverse opal structure of TiO ₂ remains.

Martinelli et al. ( M. Martinelli et al. Optical Mater. 2001, 17, 11 ) describe the preparation of inverse TiO ₂ opals using 780 nm and 3190 nm polystyrene spheres. Regular placement in a densest packed sphere is achieved by centrifuging the aqueous bead dispersion at 700-1000 rpm for 24-48 hours and then decanting, followed by air drying. The regularly arranged balls are moistened with ethanol on a filter on a Buchner funnel and then provided dropwise with an ethanolic solution of tetraethyl orthotitanate. After leaching the titanate solution, the sample is dried in a vacuum dessicator for 4-12 hours. This filling procedure is repeated 4 to 5 times. The polystyrene beads are then burned out at 600 ° C-800 ° C for 8-10 hours.

Stein et al. ( A. Stein et al. Science, 1998, 281, 538 ) describe the synthesis of inverse TiO ₂ opals starting from polystyrene spheres with a diameter of 470 nm as a template. These are produced in a 28-hour process, subjected to centrifugation and air dried. Thereafter, the latices template are applied to a filter paper. Ethanol is drawn into the latex template via a Buchner funnel attached to a vacuum pump. This is followed by dropwise addition of tetraethyl orthotitanate under suction. After drying in a vacuum desiccator for 24 h, the latices are burned out at 575 ° C. for 12 h in a stream of air.

Vos et al. ( WL Vos et al. Science, 1998, 281, 802 ) make inverse TiO ₂ opals by using polystyrene spheres with diameters of 180-1460 nm as templates. To set the densest sphere packing of the balls, a sedimentation technique is used which is supported by centrifugation for up to 48 hours. After slow evacuation to dry the template structure, it is mixed in a glovebox with an ethanolic solution of tetra-n-propoxyorthotitanate. After about 1 h, the infiltrated material is brought to the air to allow the precursor to react to TiO ₂ . This procedure is repeated eight times to ensure complete filling with TiO ₂ . Thereafter, the material is calcined at 450 ° C.

Core-shell particles whose shell forms a matrix and whose core is substantially solid and has a substantially monodisperse size distribution are disclosed in the German patent application DE-A-10145450 described. The use of such core-shell particles whose shell forms a matrix and whose core is substantially solid and has a substantially monodisperse size distribution as a template for the preparation of inverse opal structures and a method for producing inverse opal-like structures using such core-shell particles is in the International Patent Application WO 2004/031102 described. The moldings described with homogeneous, regularly arranged cavities (ie inverse opal structure) preferably have walls of metal oxides or of elastomers. Consequently, the moldings described are either hard and brittle or exhibit elastomeric character.

From the German patent application DE 10341198 is the use of core-shell particles whose shell has thermoplastic properties, for the production of moldings with homogeneous, regularly arranged cavities whose mechanical properties are particularly advantageous described. Core-shell particles whose shell forms a matrix and whose core is substantially solid and has a substantially monodisperse size distribution and whose shell is connected to the core via an intermediate layer and whose shell has thermoplastic properties, are thereby used for the production of moldings homogeneous, regularly arranged cavities used. The corresponding process for the production of moldings with homogeneous, regularly arranged cavities, is characterized in that core-shell particles whose shell forms a matrix and the core is substantially solid and has a substantially monodisperse size distribution and with the core over a Intermediate layer is connected and whose shell has thermoplastic properties, are processed by using a mechanical force and elevated temperature to moldings, preferably films and then the cores are removed. This results in moldings with homogeneous, regularly arranged cavities, which are characterized in that the regularly arranged cavities are embedded in a matrix with thermoplastic or thermosetting properties.

there it is due to the easier processability in a variant particularly preferred when arranged regularly Cavities in a matrix with thermoplastic properties embedded, wherein the matrix is preferably made of poly (styrene), thermoplastic poly (acrylate) derivatives, preferably poly (methyl methacrylate) or poly (cyclohexyl methacrylate) or thermoplastic copolymers these polymers with other acrylates, such as preferably styrene-acrylonitrile copolymers, Styrene-ethyl acrylate copolymers or methyl methacrylate-ethyl acrylate) copolymers is constructed.

In another preferred embodiment is in the Core-shell particles of the core are essentially made of one with UV radiation degradable material, preferably a UV-degradable organic Polymers, and more preferably poly (tert-butyl methacrylate), Poly (methyl methacrylate), poly (n-butyl methacrylate) or copolymers, containing one of these polymers.

Of the Shell of the core-shell particles preferably consists of the Material that later the matrix around the cavities forms.

The Removal of the cores can be done in different ways. If the cores can consist of suitable inorganic materials these are removed by etching. Preferably For example, silica cores with HF, especially dilute ones HF solution are removed. This procedure can be in turn, be preferred if before or after removal of the nuclei a cross-linking of the shell takes place. In this case, get the Sheath and thus the matrix of the molding thermoset Properties. If the cores in the core-shell particles from a UV degradable material, preferably a UV degradable material organic polymers are constructed, the removal of the Cores by UV irradiation. Again, this can happen be preferred if before or after the removal of the cores one Crosslinking of the shell takes place.

there the crosslinking can according to known methods, for example by thermally-induced or light-induced.

According to the invention preferred it is when the matrix by crosslinking of the polymeric shell of Core-shell particles using a crosslinking aid is built.

In a preferred variant of the invention, the crosslinking takes place thermally induced. In this case, it is again preferred if the sheath of the core-shell particles has free cyanate, isothiocyanate, amino, epoxide, isocyanate or hydroxyl groups and, as crosslinking assistant, a (poly) isocyanate, (poly) amine or ( Poly) epoxide is used. In this case, the crosslinking aid is selected so that it can crosslink with the reactive, complementary free functional groups by polyaddition mechanisms. in the Therefore, the combination of free hydroxyl groups in the shell with (poly) isocyanates as crosslinking aids is particularly preferred according to the invention.

In this case, it is particularly preferred if the jacket is formed by a copolymer which contains hydroxyalkyl (meth) acrylate units, such as hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate (HEMA) or hydroxybutyl methacrylate (HBMA). As crosslinking agents are in particular protected (poly) isocyanates, which are known in the trade as a polyisocyanate curing agent, and for example, sold by Bayer under the trade name Crelan ^® are.

When Polyisocyanates can be aliphatic or cycloaliphatic and aromatic isocyanates are used. As aliphatic and Cycloaliphatic isocyanates are in particular hexamethylene diisocyanate, Isophorone diisocyanate and 1,4-cyclohexyl diisocyanate used. The aromatic polyisocyanates have due to the aromatic radical a higher reactivity towards hydroxyl groups and are therefore used with particular preference. The most important Representative are tolylene diisocyanate, 4,4'-methylene diphenyl diisocyanate and 1,5-naphthalene diisocyanate.

According to the invention preferred it is, if the isocyanate function in the isocyanates in protected or blocked form is present. A suitable Protecting group is in particular ε-caprolactam. blocked The isocyanate functions can also be characterized in that Di- or oligomers of isocyanate compounds are present. So can For example, isophorone diisocyanate may be blocked as a dimer.

In In another variant of the present invention, induction takes place the crosslinking by means of light quanta, preferably with energies in Range of UV and / or VIS radiation. As a networking tool is preferably at least one photoinitiator, preferably of the Type II used.

at The bond cleavage by light energy can be compared For thermally-induced crosslinking also more stable bonds dissociative be split. For example, UV photons have a wavelength of 300 nm an energy of 400 kJ / mol.

The Depending on the requirements of the networked photoinitiators Shaped body in amounts between 0.01 and 15 wt .-%, based used on the core-shell particles and can be used individually or, for the benefit of beneficial synergistic effects, in combination be applied together.

suitable Photoinitiators should have high reactivity, synonymous with a low and therefore economical use concentration, optimal and defined light absorption, high storage stability, low toxicity, good tolerability and incorporation to unify. They are the most diverse compounds in commerce, which combine the conditions mentioned in a suitable manner, so that it does not cause the expert any difficulties, corresponding Select connections.

und bimolekular reagierenden Typ II Photoinitiatoren, wie Benzophenon-, Thioxanthon- und Campherchinon-Derivaten.A distinction is made here essentially for so-called alpha-splitters, such as hydroxyalkylphenone, benzilketal, acylphosphine oxide and aminoalkylphenone derivatives,

and bimolecular type II photoinitiators such as benzophenone, thioxanthone and camphorquinone derivatives.

According to the invention preferred is the use of photoinitiators of type II and thereby in particular the benzophenone derivatives or the basic body Benzophenone.

It it is assumed that benzophenone as a radical from an H atom The shell polymer chain can abstract, creating a more reactive Linkage point for networking arises.

In a preferred variant of the invention are additionally Sensitisers used which absorb the photon energy and forward it to the initiator. These substances take part in the reaction do not participate, but only absorb and transfer the light energy this to the initiator. Can be used for this purpose in particular to those skilled in known compounds, such as various Ketones and dyes. U include the preferred sensitizers while acetophenone, benzophenone, quinones, such as anthraquinone and duroquinone, condensed aromatics, such as pyrene and anthracene, dyes, such as Eosin, erythrosin, rose bengal, porphyrins, chlorophyll and zinc tetraphenylporphine.

there allows crosslinking with the help of photoinitiators large Degrees of freedom in the selection of the shell polymers and the processing temperatures, while thermal crosslinking here is limiting in shape acts, that the shell polymers contain thermally crosslinkable groups need and in the processing of the core-shell particles the process temperatures must be chosen so that the networking only starts after the arrangement of the cores is done; d. H. the processing temperatures should be below of 150 ° C, preferably below 100 ° C.

In a further preferred variant of the invention, the cavities are filled with a stabilizing medium, preferably a resin or silicon dioxide. Pigments based on such filled structures are characterized by particularly high mechanical stability and thus particularly easy processing. A corresponding production method in which the cavities are filled with a stabilizing medium is a further preferred embodiment of the production method according to the invention. Suitable resins are those which are also described below as a dispersion matrix. The resins are preferably resins for paint dispersions or adhesives. Silica can be produced by processes known per se in the cavities; For example, a water glass solution or a solution of tetraethoxysilane can be introduced into the cavities and then condensed out there.

invention Pigments are common in all pigments Application areas. Among the preferred applications include paints, varnishes (automotive and industrial coatings), powder coatings, Inks and toners, the direct pigmentation of plastics and varnishes and the production of masterbatches, as well as the use in cosmetic preparations.

One Another object of the present invention are preparations containing at least one diffractive colorant pigment and at least a suitable carrier. In this case, preparations are preferred in which the total amount of the diffractive colorant pigment (s) from the range of 0.1% by weight to 30% by weight, based on the total weight the preparation is selected.

usual Preparations are dispersions which are binders as carriers and optionally contain solvents.

preferred Binders are in organic solvents or in water (Water-based paints) readily soluble or dispersible; one differentiates while in water-soluble binders and in more significant water-dispersible binders. For reaction paints, z. B. polyurethane paints, apply the monomeric or oligomeric starting materials such as polyisocyanates, Epoxy resins, polyols and styrene in the form of crosslinkers, film formers and Reactive diluents as components of the binder.

critical for the binders of chemically curing systems is their responsiveness, d. H. the number of reactive Groupings (eg hydroxy groups, double bonds) in the molecule, which enables them to polyreactions. The reactivity on the one hand is responsible for a quick and complete Curing the paint film, on the other hand, it determines, for. B. reaction coats, the pot life.

To Their origin can be between natural (natural Resins) and synthetic binders (synthetic resins) become.

natural Binders: Already in antiquity were for the protection of houses and devices "coating materials" Base of tree resins, beeswax, egg yolk, quark and oils used. Some natural resins, especially rosin and its derivatives, Shellac and oils have their importance as starting materials for Binders in specific applications in addition to synthetic Keep products. Your chemical and physical indicators sometimes show considerable fluctuations due to their different origins. oils win for ecological reasons as a renewable Raw materials are again important. Among the modified natural Binders play a role in the cellulose derivatives, also the modified rosin as well as bitumen, tars and asphalts.

synthetic Binder: The large group of synthetic binders can basically after the three from the macromolecular Chemistry known reaction mechanisms are divided into polycondensation resins, Polymerization resins and polyaddition resins.

In physically drying coating materials become high molecular weight Binders of molecular weights> 500,000 used so that to achieve the required processing viscosity a solvent content of up to 90% is necessary. chemical Curing systems contain low molecular weight binders, which polymerize during film formation by chemical reaction and lead to highly cross-linked coatings. you need Solvent content in the paint of less than 60%. To the latter also include the important, designed for powder coatings solvent-free, reactive binder.

Commercially available binders are never pure chemical compounds, but technical products. By introducing hydrophilic or reactive groups or by blocking them, by esterification, etherification, copolymerization or mixing with other polymers binders are synthesized, which can be processed in solvent-based paints, water-based paints, UV-curing systems or powder coatings and the respective requirements for the coating materials and the coating made from them correspond to

usual Binders are, for example, alkyd resin, acrylic resin, bitumen, cellulose acetate, Cellulose acetobutyrate, cellulose acetopropionate, cellulose nitrate, Epoxy resin, epoxy resin ester, epoxy resin / tar combination, ethylene vinyl acetate, Melamine-formaldehyde resin, chlorinated polyethylene (see chlorinated Polyolefins), phenol-formaldehyde resin (see phenolic resins), polymethylmethacrylate, Polypropylene, polystyrene, polytetrafluoroethylene, polyurethane, polyurethane / tar combination, Polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, chlorinated Polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated rubber, Cyclic rubber, polystyrene with elastomer based on butadiene, silicone polymer, saturated polyester, tar, formaldehyde-urea resin and unsaturated polyesters.

When Binders can also be water-soluble high molecular weight organic compounds with polar groups, such as polyvinylpyrrolidone, Copolymers of vinyl propionate or acetate and vinyl pyrrolidone, partially saponified Copolymeriste of an acrylic ester and acrylonitrile, Polyvinyl alcohols with different residual acetate content, cellulose ethers, Gelatin, block copolymers, modified starch, low molecular weight, carbon- and / or sulfonic acid-containing polymers or mixtures of these substances.

Especially preferred protective colloids are polyvinyl alcohols having a residual acetate content from below 35, in particular 5 to 39 mol .-% and / or vinylpyrrolidone / vinyl propionate copolymers with a vinyl ester content of less than 35, in particular 5 to 30 wt .-%.

It may be nonionic or ionic emulsifiers, if necessary also used as a mixture. Preferred emulsifiers are optionally ethoxylated or propoxylated longer-chain alkanols or alkylphenols having different degrees of ethoxylation or propoxylation (eg adducts with 0 to 50 moles of alkylene oxide) or their neutralized, sulfated, sulfonated or phosphated derivatives. Also neutralized Dialkylsulfosuccinic or Alkyidiphenyloxiddisulfonate are particularly suitable.

Especially advantageous combinations of these emulsifiers with the above Protective colloids, as with them very finely divided dispersions to be obtained.

According to the invention the dispersions are also designed as radiation-curable coatings be. The formulation of the coating materials, printing inks etc., the type and intensity of radiation and the apparatus Arrangement of the radiation sources on the substrate to be coated be coordinated. Construction and position of coating units, web / sheet guide, Balance of temperature and humidity, viscosity and many other parameters must form a system. usual Formulations for radiation-curable coatings, Adhesives and sealants consist of a mixture of oligomers Binders (resin), monomeric reactants (crosslinking component), monomeric diluents (reactive diluents for viscosity adjustment), Photoinitiators (only for UV curing) and auxiliary agents (not involved in networking).

The Main component of the cured system is the oligomeric Partner. Proven binders for this are the unsaturated polyesters, epoxy resins, polyurethanes, polysiloxanes, Cellulose, etc. At the ends of these chemical base molecules is one or more acrylic or methacrylic groups bound. At reach such chain ends with a stable double bond H2C = CH- the high-energy rays. Radiation-curing coating materials and printing inks often contain as binders acrylate prepolymers (Acrylate oligomers) dissolved in monomeric acrylates, or unsaturated polyester dissolved in styrene. about the monomeric reactive diluents also used, the When the reaction is incorporated into the film, not only is the viscosity controlled the binder. Such monomers also influence the physical properties of the crosslinked polymer.

The Binder concepts for radiation-curing systems Although in many ways the same for other Paint and ink formulations based, there are, however also some peculiarities, as follows from the following compilation. The acrylate prepolymers are of defined molecular size by reaction of epoxy resins (epoxy acrylates), diisocyanates (Urethane acrylates) or polyesters (polyester acrylates) with acrylic or methacrylic acid.

epoxy are the reaction product of bisphenol A and acrylic acid.

she are preferably used in primers and provide hard coatings with good stance and good chemical resistance. The Free hydroxy group causes improved pigment wetting and good Adhesion to the substrate.

urethane are obtained by reacting hydroxyacrylates with diisocyanates. They are suitable for painting flexible reasons and for open-pored finishes. The connections on Base aromatic isocyanates tend in contrast to the aliphatic to yellowing.

polyester are reaction products of saturated polyesters and Hydroxy acrylates.

she are recommended for primers, but are suitable because of their good gloss also for high gloss topcoats. you Advantage lies in a comparatively low viscosity, which allows a formulation with low monomer content.

melamine are obtained by reacting melamine with acrylamide, which is modified by oleic acid amide. The solubility decreases with increasing acrylic content, so that from 2.5 moles of acrylamide additional solvents necessary.

In H2C = CH- (acrylic) by H2C = C (CH3) - (methacryl-) be replaced.

When Solvents may be present in the dispersions or usual organic solvents, individually or be used in a mixture, with the expert known common Lacquer solvents are preferably used.

Furthermore, the dispersions of the invention may also be nail varnishes. Typical nail varnishes suitable for use according to the invention consist essentially of solutions, suspensions or emulsions of certain substances. In particular, the binders, such as nitrocellulose or various synthetic resins, in particular polyacrylates, polymethacrylates, toluenesulfonamide-formaldehyde resins, toluenesulfonamide-epoxy resins, alkyd resins or polyvinyl acetate, may be mentioned here. Furthermore, nail varnishes usually contain suitable solvents for the binders, solvent mixtures usually being used. Typical solvents besides water are alcohols, esters and ketones, in particular methyl, ethyl, propyl and butyl acetate, isopropyl alcohol and n-butyl alcohol. The nail polishes may optionally with other additives for the design of the visual appearance, z. B. be added to soluble dyes. In addition, plasticizers (such as camphor or dibutyl phthalate) and by-products (eg, toluene or xylene) may be included in the mixture. These nail varnishes harden by evaporation of the solvent and the other volatile constituents, depending on the layer thickness of the paint, the temperature and the type of solvent. In addition, the curing time is dependent on other influences (eg air inflow).

In particular according to the invention Preference is given to nail care products based on water, preferably Polyurethanes or polyacrylates as binders.

water-based Nail varnishes contain, in addition to water, water-soluble resins, such as polyurethane resins, acrylic resins, alkyd resins, epoxy resins or melamine resins. The resin is preferably chosen such that that it is water soluble, white in water or appears transparent, inexpensive and easy to process is, if possible, non-flammable and non-toxic or hyperallergenic is. It can be essential that the paint dries quickly is and good film-forming properties at temperatures from 10 ° C having.

The Concentration of the diffractive colorant pigment in the pigment to be pigmented Application system d. H. the dispersion is usually between 0.1 and 70 wt .-%, preferably between 0.1 and 50 wt .-% and in particular between 1.0 and 20 wt .-%, based on the total solids content of the system.

Furthermore, the preparations according to the invention may also contain further dyes and color pigments. The dyes and pigments can be selected from the corresponding positive list of the Cosmetics Regulation or EC List of cosmetic colorants. In most cases, they are identical to the food-approved dyes. Examples of advantageous color pigments are titanium dioxide, mica, iron oxides (eg Fe ₂ O ₃ , Fe ₃ O ₄ , FeO (OH)) and / or tin oxide. Advantageous dyes are, for example, carmine, Berlin blue, chrome oxide green, ultramarine blue and / or manganese violet. It is particularly advantageous to choose the dyes and / or color pigments from the following list. The Color Index numbers (CIN) are the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971 taken. Chemical or other name CIN colour Pigment Green 10006 green Acid Green 1 10020 green 2,4-Dinitrohydroxynaphthalin-7-sulfonic acid 10316 yellow Pigment Yellow 1 11680 yellow Pigment Yellow 3 11710 yellow Pigment Orange 1 11725 orange 2,4-dihydroxyazobenzene 11920 orange Solvent Red 3 12010 red 1- (2'-chloro-4'-nitro-1'-phenylazo) -2-hydroxynaphthalene 12085 red Pigment Red 3 12120 red Ceresrot; Sudan Red; Fat Red G 12150 red Pigment Red 112 12370 red Pigment Red 7 12420 red Pigment Brown 1 12480 brown 4- (2'-methoxy-1'-phenylazo-5'sulfonsäurediethylamid) -3-hydroxy-5 '' - chloro-2 '', 4 '' - dimethoxy-2-naphthoic acid anilide 12490 red Disperse Yellow 16 12700 yellow 1- (4-Sulfo-1-phenylazo) -4-aminobenzene-5-sulfonic acid 13015 yellow 2,4-dihydroxy-azobenzene-4'-sulfonic acid 14270 orange 2- (2,4-Dimethylphenylazo-5-sulfonic acid) -1-hydroxynaphthalene-4-sulfonic acid 14700 red 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid 14720 red 2- (6-sulfo-2,4-xylylazo) -1-naphthol-5-sulfonic acid 14815 red 1- (4'-sulfophenylazo) -2-hydroxynaphthalene 15510 orange 1- (2-sulfonic acid 4-chloro-5-carboxylic acid-1-phenylazo) -2-hydroxynaphthalene 15525 red 1- (3-methyl-phenylazo-4-sulfonic acid) -2-hydroxynaphthalene 15580 red 1- (4 ', (8') - Sulfosäurenaphthylazo) -2-hydroxynaphthalene 15620 red 2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid 15630 red 3-hydroxy-4-phenylazo-2-naphthylcarboxylic acid 15800 red 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid 15850 red 1- (2-sulfo-4-methyl-5-chloro-1-phenylazo) -2-hydroxynaphthalene-3-carboxylic acid 15865 red 1- (2-sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid 15880 red 1- (3-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15980 orange 1- (4-Sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid 15985 yellow Allura Red 16035 red 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid 16185 red Acid Orange 10 16230 orange 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid 16255 red 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6,8-tisulfosäure 16290 red 8-amino-2-phenylazo-1-naphthol-3,6-disulfonic acid 17200 red Acid Red 1 18050 red Acid Red 155 18130 red Acid Yellow 121 18690 yellow Acid Red 180 18736 red Acid Yellow 11 18820 yellow Acid Yellow 17 18965 yellow 4- (4-Sulfo-1-phenylazo) -1- (4-sulfophenyl) -5-hydroxypyrazolon-3-carboxylic acid 19140 yellow Pigment Yellow 16 20040 yellow 2,6- (4'-sulfo-2 '', 4 '' - dimethyl) bis-phenylazo) 1,3-dihydroxybenzene 20170 orange Acid Black 1 20470 black Pigment Yellow 13 21100 yellow Pigment Yellow 83 21108 yellow Solvent Yellow 21230 yellow Acid Red 163 24790 red Acid Red 73 27290 red 2- [4 '- (4''-sulfo-1''- phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-7-aminonaphthalene-3,6-disulfonic acid 27755 black 4- [4 '' - sulfo-1 '' - phenylazo) -7'-sulfo-1'-naphthylazo] -1-hydroxy-8-acetyl-aminonaphthalene-3,5-disulfonic acid 28440 black Direct Orange 34, 39, 44, 46, 60 40215 orange Food Yellow 40800 orange trans-β-apo-8'-carotenaldehyde (C ₃₀ ) 40820 orange trans-apo-8'-carotenoic acid (C ₃₀ ) ethyl ester 40850 orange canthaxanthin 40850 orange Acid Blue 1 42045 blue 2,4-disulfo-5-hydroxy-4'-4 '' - bis (diethylamino) triphenylcarbinol 42051 blue 4 - [(- 4-N-ethyl-p-sulfobenzylamino) -phenyl- (4-hydroxy-2-sulfophenyl) - (methylene) -1- (N-ethylN-p-sulfobenzyl) -2,5-cyclohexadienimine] 42053 green Acid blue 7 42080 blue (N-ethyl-p-sulfobenzylamino) -phenyl- (2-sulfophenyl) -methylene- (N-ethyl-N, p-sulfobenzyl) Δ ^2,5- cyclohexadiene imine 42090 blue Acid Green 9 42100 green Diethyl-di-sulfobenzyl-di-4-amino-2-chloro-di-2-methylfuchsonimmonium 42170 green Basic Violet 14 42510 violet Basic Violet 2 42520 violet 2'-methyl-4 '- (N-ethyl-Nm-sulfobenzyl) amino-4''- (N-diethyl) amino-2-methyl-N-ethyllN-m-sulfobenzylfuchsonimmonium 42735 blue 4 '- (N-Dimethyl) amino-4''- (N-phenyl) -aminonaphtho-N-dimethylfuchsonimmonium 44045 blue 2-hydroxy-3,6-disulfo-4,4'-bis-dimethylaminonaphthofuchsonimmonium 44090 green Acid Red 52 45100 red 3- (2'-methylphenylamino) -6- (2'-methyl-4'-sulfophenylamino) -9- (2 '' - carboxyphenyl) -xantheniumsalz 45190 violet Acid Red 50 45220 red Phenyl-2-oxyfluoron-2-carboxylic acid 45350 yellow 4.5-Dibromofluorescein 45370 orange 2,4,5,7-Tetrabromfluorescein 45380 red Solvent dye 45396 orange Acid Red 98 45405 red 3 ', 4', 5 ', 6'-tetrachloro-2,4,5,7-tetrabromfluorescein 45410 red 4.5-Diiodfluorescein 45425 red 2,4,5,7-tetraiodofluorescein 45430 red quinophthalone 47000 yellow Quinophthalone disulphonic 47005 yellow Acid Violet 50 50325 violet Acid Black 2 50420 black Pigment Violet 23 51319 violet 1,2-dioxyanthraquinone, calcium-aluminum complex 58000 red 3-Oxypyren-5,8,10-sulfonic acid 59040 green 1-hydroxy-4-N-phenyl-aminoanthraquinone 60724 violet 1-hydroxy-4- (4'-methylphenylamino) anthraquinone 60725 violet Acid Violet 23 60730 violet 1,4-di (4'-methylphenylamino) anthraquinone 61565 green 1,4-bis (o-sulfo-p-toluidino) anthraquinone 61570 green Acid Blue 80 61585 blue Acid Blue 62 62045 blue N, N'-dihydro-1,2,1 ', 2'-anthrachinonazin 69800 blue Vat Blue 6; Pigment Blue 64 69825 blue Vat Orange 7 71105 orange indigo 73000 blue Indigo-disulfonic 73015 blue 4,4'-dimethyl-6,6'-dichlorothioindigo 73360 red 5,5'Dichlor-7,7'-dimethylthioindigo 73385 violet Quinacridone Violet 19 73900 violet Pigment Red 122 73915 red Pigment Blue 16 74100 blue phthalocyanines 74160 blue Direct Blue 86 74180 blue Chlorinated phthalocyanines 74260 green Natural Yellow 6, 19; Natural Red 1 75100 yellow Bixin, nor-bixin 75120 orange lycopene 75125 yellow trans-alpha, bet or gamma-carotene 75130 orange Keto and / or hydroxyl derivatives of carotene 75135 yellow Guanine or pearlescing agent 75170 White 1,7-bis (4-hydroxy-3-methoxyphenyl) 1,6-heptadiene-3,5-dione 75300 yellow Complex salt (Na, Al, Ca) of karmic acid 75470 red Chlorophyll a and b; Copper compounds of chlorophylls and chlorophyllins 75810 green aluminum 77000 White alumina hydrate 77002 White Water-containing aluminum silicates 77004 White ultramarine 77007 blue Pigment Red 101 and 102 77015 red barium sulfate 77120 White Bismuth oxychloride and its mixtures with mica 77163 White calcium carbonate 77220 White calcium sulphate 77231 White carbon 77266 black Pigment Black 9 77267 black Carbo medicinalis vegetabilis 77268: 1 black chromium 77288 green Chromium oxide, hydrous 77278 green Pigment Blue 28, Pigment Green 14 77346 green Pigment Metal 2 77400 brown gold 77480 brown Iron oxides and hydroxides 77489 orange iron oxide 77491 red iron oxide 77492 yellow iron oxide 77499 black Mixtures of iron (II) and iron (III) hexacyahoferrate 77510 blue Pigment White 18 77713 White Mangananimoniumdiphosphat 77742 violet Manganese phosphate; Mn ₃ (PO ₄ ) ₂ .7H ₂ O 77745 red silver 77820 White Titanium dioxide and its mixtures with mica 77891 White zinc oxide 77947 White 6,7-dimethyl-9- (1'-D-ribityl) -isoalloxazine, lactoflavin yellow caramel brown Capsanthin, Capsorubin orange betanin red Benzopyrylium salts, anthocyanins red Aluminum, zinc, magnesium and calcium stearate White Bromthymolblau blue

It may also be favorable to choose as the dye one or more substances from the following group:
2,4-dihydroxyazobenzene, 1- (2'-chloro-4'-nitro-1'phenylazo) -2-hydroxynaphthalene, ceric red, 2- (4-sulfo-1-naphthylazo) -1-naphthol-4-sulfonic acid, Calcium salt of 2-hydroxy-1,2'-azonaphthalene-1'-sulfonic acid, calcium and barium salts of 1- (2-sulfo-4-methyl-1-phenylazo) -2-naphthylcarboxylic acid, calcium salt of 1- (2- Sulfo-1-naphthylazo) -2-hydroxynaphthalene-3-carboxylic acid, aluminum salt of 1- (4-sulfo-1-phenylazo) -2-naphthol-6-sulfonic acid, aluminum salt of 1- (4-sulfo-1-naphthylazo) -2-naphthol-3,6-disulfonic acid, 1- (4-sulfo-1-naphthylazo) -2-naphthol-6,8-disulfonic acid, aluminum salt of 4- (4-sulfo-1-phenylazo) -2- ( 4-sulfophenyl) -5-hydroxy-pyrazolone-3-carboxylic acid, aluminum and zirconium salts of 4,5-dibromofluorescein, aluminum and zirconium salts of 2,4,5,7-tetrabromofluorescein, 3 ', 4', 5 ', 6'-Tetrachloro-2,4,5,7-tetrabromo-fluorescein and its aluminum salt, aluminum salt of 2,4,5,7-tetraiodofluorescein, aluminum salt of quinophthalone-disulfonic acid, aluminum salt of indigo-disulfonic acid, red and the like and black iron oxide (CIN: 77,491 (red) and 77,499 (black)), iron oxide hydrate (CIN: 77,492), manganese ammonium diphosphate, and titanium dioxide.

Further advantageous are oil-soluble natural dyes, such as z. As paprika extract, β-carotene or cochineal.

• 1. Natürliche Perlglanzpigmente, wie z. B. 1. ”Fischsilber” (Guanin/Hypoxanthin-Mischkristalle aus Fischschuppen) und 2. ”Perlmutt” (vermahlene Muschelschalen)
• 2. Monokristalline Perlglanzpigmente wie z. B. Bismuthoxychlorid (BiOCl)
• 3. Schicht-Substrat Pigmente: z. B. Glimmer/Metalloxid Basis für Perlglanzpigmente sind beispielsweise pulverförmige Pigmente oder Ricinusöldispersionen von Bismutoxychlorid und/oder Titandioxid sowie Bismutoxychlorid und/oder Titandioxid auf Glimmer. Insbesondere vorteilhaft ist z. B. das unter der CIN 77163 aufgelistete Glanzpigment.

Also advantageous is the combination with pearlescent pigments. Particularly preferred are the types of pearlescent pigments listed below:

• 1. Natural pearlescent pigments, such as. B. 1. "fish-silver" (guanine / hypoxanthine mixed crystals from fish scales) and 2. "mother-of-pearl" (ground mussel shells)
• 2. Monocrystalline pearlescent pigments such. B. bismuth oxychloride (BiOCl)
• 3rd layer substrate pigments: z. B. Mica / metal oxide base for pearlescent pigments are, for example, powdered pigments or castor oil dispersions of bismuth oxychloride and / or titanium dioxide and bismuth oxychloride and / or titanium dioxide on mica. Particularly advantageous is z. For example, listed under the CIN 77163 luster pigment.

Also advantageous, for example, are the following pearlescent pigment types based on mica / metal oxide: group Coating / colour Silver-white pearlescent pigments TiO ₂ : 40-60 nm silver interference pigments TiO ₂ : 60-80 nm yellow TiO ₂ : 80-100 nm red TiO ₂ : 100-140 nm blue TiO ₂ : 120-160 nm green Color Luster Pigments Fe ₂ O ₃ bronze Fe ₂ O ₃ copper Fe ₂ O ₃ red Fe ₂ O ₃ red violet Fe ₂ O ₃ Red Green Fe ₂ O ₃ black combination pigments TiO ₂ / Fe ₂ O ₃ golds TiO ₂ / Cr ₂ O ₃ green TiO ₂ / Berlin Blue deep blue

Especially preferred are z. As the Merck under the trade name Timiron, Colorona, Dichrona, Xirona and Ronastar available Pearlescent pigments.

Of course, the list of pearlescent pigments mentioned should not be limiting. Pearlescent pigments which are advantageous in the context of the present invention are obtainable in numerous ways known per se. For example, other substrates except mica can be coated with other metal oxides such. As silica and the like. Advantageous z. B. with TiO ₂ and Fe ₂ O ₃ coated SiO ₂ particles ("Ronaspheren"), which are sold by Merck and are particularly suitable for the optical reduction of fine wrinkles.

It may also be advantageous to completely dispense with a substrate such as mica. Particularly preferred are pearlescent pigments which are prepared using SiO ₂ . Such pigments, which may also have additional gonichromatic effects are, for. B. under the trade name Sicopearl Fantastico available from BASF.

Farther Pigments from Engelhard / Mearl can advantageously be used Base of calcium sodium borosilicate, which is coated with titanium dioxide are to be used. These are available under the name Reflecks. They have a particle size of 40-80 μm a glittering effect in addition to the color.

Especially Also advantageous are also effect pigments which are sold under the trade name Metasomes Standard / Glitter in different colors (yellow, red, green, blue) are available from Flora Tech. The glitter particles lie in mixtures with different ones Auxiliaries and dyes (such as the dyes with the Color Index (CI) numbers 19140, 77007, 77289, 77491).

The Dyes and pigments can be used individually as well be present in a mixture and be mutually coated with each other, being different coating thicknesses in general different color effects are caused. The total amount of Dyes and coloring pigments will be beneficial in the field from Z. From 0.1% to 30% by weight, preferably from 0.5 to 15 Wt .-%, in particular from 1.0 to 10 wt .-% chosen, respectively based on the total weight of the preparations.

Also without further explanation it is assumed that a person skilled in the art can make the most of the above description. The preferred embodiments are therefore only as descriptive, in no way as limiting in any way To understand the revelation. The complete revelation of all above and below listed applications and publications are incorporated by reference into this application. The The following examples illustrate the present invention. she however, are not to be considered limiting. All connections or components that can be used in the preparations, are either known and available for purchase or can be synthesized by known methods. Some of the INCI names of the raw materials used are given (The INCI names are by definition in English Language specified).

Examples

Used abbreviations:

ALMA

allyl methacrylate

AT

acrylonitrile

APS

ammonium

BDDA

Butane-1,4-diol diacrylate

CHMA

cyclohexyl

HEMA

Hydroxyethalmethacrylat

MMA

methyl methacrylate

SDS

Dodecyl sulfate sodium salt

SDTH

sodium

PCHMA

Poly (cyclohexyl methacrylate)

PS

Poly (styrene)

Example 1 Preparation of spheres as primary building blocks

Example 1a: Preparation of monodisperse Silica spheres of diameter 250 nm

In a flask, 1140 ml of ethanol and 430 ml of demineralized water are presented. With gentle stirring, the mixture is heated to 63 ° C. Then 266 ml of 25% ammonia solution are added. While stirring vigorously, 168 ml of tetraethyl orthosilicate (also heated to 63 ° C.) are added all at once and rapidly. After stirring for 15 seconds, the stirring is stopped and the dispersion allowed to stand for 18 h. After concentrating the dispersion, an azeotropic distillation is carried out to remove the ethanol and the ammonia, so that the SiO ₂ spheres are in a purely aqueous dispersion.

Example 1b: Preparation of monodisperse PMMA balls of a diameter of 300 nm

One Round bottom flask is charged with 540 ml of distilled water and 100 ml of methyl methacrylate fed. After heating to 80 ° C, a nitrogen gas cushion added to the dispersion. The impeller stirrer opens 300 rpm, followed by 0.5 g of 2,2'-azobis (2-methylpropionamidine) dihydrochloride should admit. After 2 h, the reaction is complete and the contents of the flask is cooled. The product is made by centrifuging several times and decanting cleaned.

Example 2: Organization of the balls in a colloid-crystalline packing (opal packing)

The Dispersions from Example 1a or 1b are over a Büchner funnel with fine filter paper over water jet pump vacuum aspirated. First, the colloidal spheres pass through the filter chute (recognizable by the turbid filtrate), but it is fast a partial blockage of the filter pores, so that only the Water is sucked off and the balls are returned as filter cake stay. The regular arrangement of the balls creates dazzling color effects.

Example 3: Preparation of inverse opaline color particles

10 g of the starting from Example 1b in Example 2 made of PMMA colloid spheres, iridescent filter cake with a precursor solution consisting of 2 ml of tetraethoxysilane, 2 ml of tetra-t-butyl titanate, 0.7 ml of conc. HCl, 3 ml of ethanol and 2 ml of water impregnated under low vacuum suction. The loaded filter cake is dried for 1 h and then treated in an oven as follows: step 1 2 3 4 Starting temperature [° C] 20 100 350 550 Heating rate [° C / h] 40 60 66 600 Target temperature [° C] 100 350 550 20 Holding period [h] 2 h 2 h 300 h /

in this connection The PMMA spheres are pyrolytically degraded and remain iridescent colored particles from inverse opals back.

Example 4: Stabilization of the Opal Matrix

The Particles from Example 3 are mixed with a thin liquid UV-curable adhesive dispersion (NOA61, Norland) impregnated and the adhesive cured by UV irradiation. The resulting powder is placed in a ball mill Grinding cooling to pigments.

Example 5: Preparation of inverse opaline color particles

Precursor solutions are prepared according to the following scheme:
10 g of tetraethoxysilane, 0.8 ml of conc. HCl and 5.4 ml of ethanol are ripened at 37 ° C for 10 minutes. At 0 ° C then Al-tris-sec-butoxide or tetraethoxytitanium are added.

The following mixing ratios are set: Si: Ti 10: 1 5: 1 3: 1 2: 1 1: 1 Si: Al 10: 1 5: 1 3: 1 2: 1

Finally, 1 ml of water is added and the mixture is allowed to rest for 20 hours. The resulting clear solution is diluted 1.1 with ethanol so that under mild vacuum suction 10 g of starting from Example 1b in Example 2 made of PMMA colloid spheres, iridescent filter cake impregnated. The loaded filter cake is dried for 1 h and then treated in an oven as follows: step 1 2 3 4 Starting temperature [° C] 20 100 350 550 Heating rate [° C / h] 40 60 66 600 Target temperature [° C] 100 350 550 20 Holding period [h] 2 h 2 h 300 h /

in this connection The PMMA spheres are pyrolytically degraded and remain iridescent colored particles from inverse opals back.

Example 6: Stabilization of the Opal Matrix

Example 6a: UV-curable matrix

The Particles from example 5 are mixed with a thin liquid UV-curable adhesive dispersion (NOA61, Norland) impregnated and the adhesive cured by UV irradiation. The resulting powder is placed in a ball mill Grinding cooling to pigments.

Example 6b: Silica matrix

10 g of the particles from Example 5 are in a beaker with 6 g Tetraethoxysilane impregnated. Then 100 ml of water added and the beaker carefully swung. Now it will by adding ammonia solution while stirring the pH the dispersion is adjusted to 9. After 30 minutes, the beaker becomes including contents in a warming cabinet with a temperature converted from 80 ° C and for 30 Minutes left. The contents of the beaker are about aspirated a Büchner funnel and the filter cake carefully washed with water. The filter cake is in the oven dried and the resulting hard powder under mild conditions milled to pigments.

Example 7: Preparation of inverse opaline color particles by etching

Example 7a: Functionalization of the SiO ₂ Cores from Example 1

To 1.3 l of ethanolic suspension with 2.5% by weight SiO ₂ (SiO ₂ suspension with violet drying color (wavelength maximum 1111 = 400 nm, average particle diameter after TEM 201 nm, according to Example 1), 0.69 M NH ₃ and 2 MH ₂ O are added with stirring at room temperature 3 ml of MPS dissolved in ethanol. The mixture is slowly heated to 65 ° C. under normal pressure on a rotary evaporator. After 1.5 hours, the distillation of an azeotropic mixture of ethanol and water is started by reducing the pressure. The distilled off liquid is replaced by absolute ethanol. A total of 1.2 l of ethanol-water mixture are removed. After 2 hours, the reaction solution is concentrated to 300 ml and transferred to a 1 liter round bottom flask. 0.06 g of SDS dissolved in 120 g of water are added and distilled off again at 65.degree. C. in ethanol. The distilled off liquid is replaced by water.

Example 7b: Emulsion Polymerization

The emulsion polymerization is carried out in a double-walled, at 75 ° C thermostated 250 ml glass reactor with inert gas, propeller and reflux condenser. 110 g (containing 17 g of SiO ₂ ) SiO ₂ suspension according to Example 2 are bubbled with argon for 20 min. Then 0.1 g of SDS are added and the mixture is introduced into the reactor. Then 0.05 g of SPS dissolved in 3 g of water are added. After 15 minutes, a monomer emulsion of 5.4 g MMA, 0.6 g ALMA, 0.02 g SDS (0.33 wt% on monomer), 0.04 g KOH and 30 g water is added over a period of 90 min continuously added. The reactor contents are stirred for 20 minutes without further addition. This was followed by the addition of 0.02 g of APS dissolved in 3 g of water. After 10 minutes, a second monomer emulsion of 97.6% by weight of benzyl methacrylate and 2% by weight of hydroxyethyl methacrylate and 0.4% by weight of SDS and 40 g of water are continuously metered in over a period of 200 minutes. The almost complete reaction of the monomers is then stirred for a further 120 minutes. The core-shell particles are then precipitated in 500 ml of ethanol, the precipitate is completed by adding 15 g of concentrated aqueous saline solution, the suspension with 500 ml of dist. Added water, suction filtered and the polymer dried at 50 ° C in a vacuum.

Example 7c Preparation of the template film

The dried, pulverulent polymers from Example 14b are mixed in a micro extruder (Thermo Haake, Minilab 5, co-former) with 0.2 wt .-% Licolub Fa1 and 0.2 wt .-% Licolub WE 40 (both from Fa. Clariant ) and 3 wt .-% Crelan ^TM Ul (Bayer AG) at a temperature of 130 ° C compounded. The extrudate from the perforated nozzle is rolled up into a screw and pressed with a laboratory press (Collin) between two PET films to thin films according to the following program: step 1 2 3 4 Press time [min] 2 2 10 2 Pressure [bar] 1 50 50 50 Temp. [C °] 130 130 190 20

The films obtained are brittle and stable Swelling by solvent. Therefore we suspected that Under the pressing conditions, a chemical cross-linking of Crelans has formed with the HEMA to polyurethane structures.

The Films are ground with cooling into small particles.

Example 7d: etching of the particles with hydrofluoric acid

The Particles become in open vessels with hydrofluoric acid (10 wt .-%) overlaid and charged one week at RT. Evaporating hydrofluoric acid is replaced by fresh ones. After rinsing with water and drying, the etched show Pigments clearly visible reflection colors.

formulation Examples

In The following formulation examples are used as pigment, respectively the photonic effect materials selected from a or more of the preceding examples.

In the formulations, the trade name, the INCI name, as well as the proportion in wt .-% and a source of supply for the raw materials are given. Example A: Wet Lip Balm with 10% diffractive colorant Phase A pigment 10.00% (1) Phase B Vogelatum Equiline EU103 11.00% (2) Candelilla wax Candelilla Cera (Candelilla Wax) 7.00% (3) Bleached beeswax Cera Alba (Beeswax) 5.00% (1) Myritol 331 Cocoglycerides 8.00% (4) Ozokerite Wax White # 77W ozocerites 3.00% (3) isopropyl Isopropyl myristate 5.00% (4) Eusolex ^® 2292 Ethylhexyl methoxycinnamate, BHT 7.00% (1) Eusolex ^® OCR Octocrylene 4.00% (1) Oxynex ^® K liquid PEG-8, tocopherol, ascorbyl palmitate, ascorbic acid, citric acid 0.10% (1) Propyl-4-hydroxybenzoate Propylparaben 0.10% (1) Color dispersion in castor oil 0.50% castor oil Ricinus Communis (Castor Oil) 38.80% (5) Phase C Perfume oil Tendresse # 75418C Perfume 0.50% (6)

production:

The Phase B ingredients are stirred at 75 ° C heated until everything is melted. Add phase A and stir well. The lipstick mass then tempered at 65 ° C Fill the casting apparatus, add phase C and 15 minutes stir. The homogeneous melt is heated to 55 ° C preheated mold poured.

Subsequently Cool the molds and remove the castings cold. After warming the lipsticks to room temperature the lipsticks are briefly flamed.

Sources:

• (1) Merck KGaA / ^Rona®
• (2) Natunola Health Inc.
• (3) Ross Waxes
• (4) Cognis GmbH
• (5) Henry Lamotte GmbH
• (6) Haarmann & Reimer GmbH

Example B: shower gel Phase A pigment 0.10% (1) Keltrol T. Xanthan gum 0.75% (2)

Water, demineralized Aqua (Water) 64.95% phase B Plantacare® 2000 UP decyl glucosides 20.00% (3) Texapon.RTM ASV 50 Sodium Laureth Sulfates, Sodium Laureth-8 Sulfates, Magnesium Laureth Sulfates, Magnesium Laureth-8 Sulfate, Sodium Oleth Sulfate, Magnesium Oleth Sulfate 3.60% (3) Bronidox L Propylene Glycol, 5-bromo-5-nitro-1,3-dioxane 0.20% (3) perfume oil Everest 79658 SB Perfume 0.05% (4) 1% FD & C Blue No. 1 in water Aqua (Water), CI 42090 (FD & C Blue No. 1) 0.20% (5) phase C citric acid monohydrate Citric acid 0.15% (1) Water, demineralized Aqua (Water) 10.00%

production:

For Phase A becomes the pigment according to the invention in water is stirred. Sprinkle Keltrol T while stirring slowly and stir until dissolved. The phases B and Add C in succession, stirring slowly until everything is distributed homogeneously. Adjust the pH to 6.0 to 6.5.

Sources:

• (1) Merck KGaA / Rona®
• (2) kelco
• (3) Cognis GmbH
• (4) Haarmann & Reimer GmbH
• (5) BASF AG

Example C: Eyeshadow Phase A pigment 55.0% (1) ^Biron® B 50 CI 77163 (Bismuth Oxychloride) 3.00% (1) Colorona® ^® Dark Blue Pearlescent Pigment: Mica, CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) 10.00% (1) magnesium stearate Magnesium Stearate 2.50% (1) White tone (painted) kaolin 5.00% (1) Hubersorb 600 Calcium silicate 0.50% (2) talc Talc 11.00% (1) Phase B Amerchol L 101 Lanolin Alcohol, Paraffin Liquidum (Mineral Oil) 10.70% (3) Super Hartolan Lanolin Alcohol 1.00% (4) Ewalin 1751 petrolatum 1.00% (5) Propyl-4-hydroxy-benzo at Propylparaben 0.10% (1) Perfume oil Elegance # 79228 D MD perfume 0.20% (6)

production:

ingredients put together and premade phase A. Subsequently The powder mixture with stirring dropwise with the molten Move phase B. The powders are pressed at 40-50 bar.

Sources:

• (1) Merck KGaA / ^Rona®
• (2) J.M. Huber Corp.
• (3) Amerchol
• (4) Croda GmbH
• (5) H. Erhard Wagner GmbH
• (6) Haarmann & Reimer GmbH

Example D: Eye Shadow Gel Phase A pigment 15.00% (1) Mica Black CI 77499 (Iron Oxide), Mica, CI 77891 (Titanium Dioxide) 5.00% (1) Ronasphere ^® silica 3.00% (1) Carbopol ETD 2001 Carbomer 3.00% (2) Water, demineralized Aqua (Water) 60.00% Phase B Glycerin, anhydrous glycerin 2.00% (1) Germaben II Propylene glycol, diazolidinyl urea, methylparaben, propylparaben 0.20% (3) Triethanolamine reinst Triethanolamine 0.70% (1) Water, demineralized Aqua (Water) 13.80%

production:

Pigment and Ronasphere ^® are dispersed in the water of phase A. Acidify with a few drops of citric acid to reduce viscosity, sprinkle with Carbopol while stirring. After complete dissolution, stir in the pre-dissolved phase B slowly.

Sources:

• (1) Merck KGaA
• (2) BF Goodrich GmbH
• (3) ISP Global Technologies

Example E: Lip Gloss Phase A pigment 10.00% (1) Phase B Indopol H 100 polybutenes 59.90% (2) Bentone Gel MIO V Quaternium-18 Hectorite, Propylene Carbonate, Paraffin Liquidum (Mineral Oil) 20.00% (3) Eutanol G octyldodecanol 6.00% (4) RonaCare ™ tocopherol acetate Tocopheryl acetate 1.00% (1) Dow coming 1403 fluid Dimethiconol, dimethicone 3.00% (5) Propyl-4-hydroxybenzoate Propylparaben 0.05% (1) Rouge Covapate W 3773 Ricinus Communis (Castor Oil), CI 15850 (D & C) Red no. 6) 0.05% (6)

production:

All Phase B ingredients are weighed together to 70 ° C heated and stirred well until a homogeneous mass emerged is. Then the pigments are added and stirred again. The homogeneous mixture is filled at 50-60 ° C from.

Sources:

• (1) Merck KGaA / ^Rona®
• (2) BP Amoco
• (3) Elementis Specialties
• (4) Cognis GmbH
• (5) Dow Corning
• (6) Les Colorants Wackherr

Example F: Eyeshadow compact powder Phase A pigment 25.00% (1) Colorona® ^® Dark Blue Mica, CI 77891 (Titanium Dioxide), CI 77510 (Ferric Ferrocyanide) 5.00% (1) talc Talc 49.50% (1) Potato starch Solanium Tuberosum (Potato Starch) 7.50% (2) magnesium stearate Magnesium Stearate 2.50% (1) Phase B isopropyl Isopropyl stearate 9.14% (3) cetyl palmitate Cetyl palmitate 0.53% (1) Ewalin 1751 petrolatum 0.20% (4) Perfume oil Elegance # 79228 D MF perfume 0.20% (5) Propyl-4-hydroxybenzoate Propylparaben 0.10% (1)

production:

ingredients Phase A together and premix. Subsequently The powder mixture with stirring dropwise with the molten Move phase B. The powders are pressed at 40-50 bar.

Sources:

• (1) Merck KGaA
• (2) Südstärke GmbH
• (3) Cognis GmbH
• (4) H. Erhard Wagner GmbH
• (5) Haarmann & Reimer GmbH

Example G: Cream Mascara (O / W) Phase A Mica Black CI 77499 (Iron Oxide), Mica, CI 77891 (Titanium Dioxide) 10.00% (1) pigment 5.00% (1) Phase B stearic acid Stearic acid 8.00% (1) Bleached beeswax Cera Alba (Beeswax) 6.00% (1) Carnauba Wax 2442 L Copernicia Cerifera (Carnauba Wax) 4.00% (2) Eutanol G octyldodecanol 3.00% (3) Arlacel 83V Sorbitan sesquioleate 2.00% (4) Propyl-4-hydroxybenzoate Propylparaben 0.10% (1) RonaCareTM Tocoherolace did tocopheryl acetate 0.50% (1) Phase C Water, demineralized Aqua (Water) 50.84% Triethanolamine reinst Triethanolamine 2.30% (1) Water Soluble Shellac SSB 63 Shellac 8.00% (5) Methyl 4-hydroxybenzoate methylparaben 0.25% (1) RonaCareTM Biotin biotin 0.01% (1)

production:

All Melt constituents of phase B together at about 80 ° C, stir until everything is melted. The diffractive colorants stir in phase A. Solve Phase C Shellac in water, to 75 ° C. The remaining ingredients Phase C, solve. Slowly submerge at 75 ° C Stir phase C into phase A / B, homogenize for 2 min. Cool the mass to room temperature while stirring.

Sources:

• (1) Merck KGaA / ^Rona®
• (2) Kahl & Co.
• (3) Cognis GmbH
• (4) Uniqema
• (5) Paroxite Ltd.

Example H: nail polish Phase A pigment 2.00% (1) Thixotropic Nail Polish Base 1348 Toluene, Ethyl Acetate, Butyl Acetate, Nitrocellulose, Tosylamide / Formaldehyde Resin, Dibutyl Phthalate, Isopropyl Alcohol, Stearalkonium Hectorite, Camphor, Acrylate Copolymer, Benzophenone-1 98.00% (2) Color dispersion with nitrocellulose Lacquer (qs)

production:

The invention is used together with the Lackbase weighed, mixed well with a spatula by hand and then Stirred for 10 min at 1000 rpm.

Sources:

• (1) Merck KGaA / ^Rona®
• (2) International Lacquers S.A.

Example J: shampoo Phase A pigment 0.05% (1) Carbopol ETD 2020 Acrylates / C10-30 alkyl acrylates Crosspolymer 0.90% (2) Water, demineralized Aqua (Water) 59.90% Phase B Triethanolamine reinst Triethanolamine 0.90% (1) Water, demineralized Aqua (Water) 10.00% Phase C Plantacare 2000 UP Decyl glucosides 20.00% (3) Texapon ASV Magnesium Oleth Sulfate, Sodium Oleth Sulfate, Magnesium Laureth-8 Sulfates, Sodium Laureth-8 Sulfates, Magnesium Laureth Sulfate, Sodium Laureth Sulfate 8.00% (3) Bronidox L Propylene glycol, 5-bromo-5-nitro-1,3-dioxane 0.20% (3) Perfume oil Everest 79658 SB Perfume 0.05% (4)

production:

For Phase A, the pigment of the invention in the water Stir. With a few drops of citric acid (10%) acidify to reduce the viscosity and the Slowly sprinkle Carbopol while stirring. After complete Slowly add solution to Phase B. One after another will be now the ingredients of phase C are added.

Sources:

• (1) Merck KGaA
• (2) BF Goodrich GmbH
• (3) Cognis GmbH
• (4) Haarmann & Reimer GmbH

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - DE 10145450 A [0018]
• WO 2004/031102 [0018]
• - DE 10341198 [0019]

Cited non-patent literature

• K. Busch et al. Phys. Rev. Letters E, 198, 50, 3896 [0007]
• - V. Colvin et al. Adv. Mater. 2001, 13, 180 [0013]
• - De La Rue et al. Synth. Metals, 2001, 116, 469 [0014]
• M. Martinelli et al. Optical Mater. 2001, 17, 11 [0015]
• - A. Stein et al. Science, 1998, 281, 538 [0016]
• - WL Vos et al. Science, 1998, 281, 802 [0017]
• Rowe Color Index, Third Edition, Society of Dyers and Colourists, Bradford, England, 1971 [0070]

Claims (14)

Diffractive colorant pigment used in the the optical properties essentially share substantially from arrangements of spherical cavities with a essentially monodisperse size distribution. Pigment according to claim 1, characterized in that that the pigments are platelets or spheres whose thickness is preferably in the range of 0.5 to 20 μm, particularly preferably in the range 1 to 10 microns. Pigment according to one or more of the preceding Claims, characterized in that the matrix around the Cavities essentially of an inorganic material, preferably a metal or semimetal or a metal chalcogenide or metal pnictide, in particular aluminum oxide, zirconium oxide, Titanium dioxide, ceria, or mixtures or mixed oxides thereof or Mixtures or mixed oxides thereof with silica are preferred. Pigment according to one or more of the preceding Claims, characterized in that the the matrix around the cavities essentially of crosslinked polymers consists. Pigment according to one or more of the preceding Claims, characterized in that the average diameter the cavities in the diffractive colorants in the range of about 50-500 nm, preferably in the range of 100-500 nm and most preferably in the range of 200 to 280 nm. Pigment according to one or more of the preceding Claims, characterized in that the cavities with a stabilizing medium, preferably a resin or Silica are filled. Preparation containing at least one diffractive colorant pigment according to one or more of the preceding claims and at least one suitable carrier. Preparation according to claim 7, characterized the total amount of diffraction colorant pigment (s) is in the range of 0.1% to 30% by weight, based on the total weight of Preparation, is chosen. Process for the preparation of a preparation for topical Use, characterized in that at least one diffractive colorant pigment according to one or more of the preceding claims at least one suitable carrier and optionally further Ingredients is mixed. Process for the preparation of a diffractive colorant pigment, wherein in a first step, a three-dimensional sphere package is generated, in a second step, the matrix around the ball aggregates is built and in a third subsequent or simultaneous Step the ball aggregates are removed and in a fourth Step, the resulting shaped body crushed into pigments become. Method according to claim 10, characterized in that that the matrix by cross-linking the polymeric shell of core-shell particles is built using a crosslinking aid. A method according to claim 11, characterized that the crosslinking is thermally induced and the mantle of the Core-shell particles free cyanate, isothiocyanate, amino, epoxide, Isocyanate or hydroxy groups and as a crosslinking aid a (poly) isocyanate, (poly) amine or (poly) epoxide is used, wherein the jacket is preferably formed by a copolymer, which contains hydroxyalkyl (meth) acrylate units, and it the crosslinking aid is preferably an isocyanate, in particular preferably a protected isocyanate is. A method according to claim 11, characterized that the networking by means of light quanta, preferably with energies in the range of UV and / or VIS radiation, is induced and it The crosslinking aid is preferably at least one Photoinitiator of the type II and thereby particularly preferably at least a benzophenone derivative or benzophenone. Method according to one or more of the preceding Claims, characterized in that the cavities with a stabilizing medium, preferably a resin or Be filled silica.