DE102008045308A1 - Producing coatings, comprises applying a dispersion of diffraction colorant precursors on the surface - Google Patents

Abstract

Producing coatings with opalescent effect, comprises applying a dispersion of diffraction colorant precursors on the surface. Independent claims are included for: (1) the dispersion comprising diffraction colorant precursors (1-80 wt.%), binder (1-50 wt.%), solvent (10-98 wt.%) and optionally other auxiliary materials; and (2) a process for preparing a dispersion for the surface application, comprising mixing at least a diffraction colorant precursor with at least one suitable carrier and at least one binder, and optionally other auxiliary materials.

Description

The The invention relates to the production of laminar coatings with an opalescent effect, preparations containing diffractive colorant precursors and process for the preparation of the preparations and their use.

Diffractive colorants For the purposes of the present invention, materials are the photonic Have structures. Among photonic structures i. a. Understood a regular modulation of the systems Dielectric constant (and thereby also the refractive index) exhibit. Corresponds to the periodic modulation length in about the wavelength of the (visible) light, so occurs the structure interacts with the light in the manner of a diffraction grating, which manifests itself in angle-dependent color phenomena.

In usually such diffractive colorants exist in the the optical properties essentially share substantially from arrangements of spherical particles or cavities with a substantially monodisperse size distribution.

One An example of this is the naturally occurring gemstone Opal made of a densely packed ball of silica balls exists and intervening cavities containing air, silica gel or water are filled. Natural precious opals are composed of domains consisting of monodisperse, densely packed and therefore regularly arranged Silica gel balls with diameters of 150-400 nm. The play of colors this opal comes through Bragg-like scattering of the incident Light at the lattice planes of the crystal-like domains conditions.

Appropriate Ball arrangements can of course also with balls be obtained from other materials. Suitable stabilization methods for ball aggregates are known from the literature.

US 4,703,020 describes a method for producing a decorative material consisting of amorphous silica beads arranged three-dimensionally with zirconia or zirconium hydroxide in the interstices between the beads. The beads have a diameter of 150-400 nm. The preparation is carried out in two stages. In a first step, silica spheres are allowed to sediment from an aqueous suspension. The resulting mass is then dried in air and then calcined at 800 ° C. The calcined material is introduced into the solution of a zirconium alkoxide in a second step, whereby the alkoxide penetrates into the interstices between the cores and zirconia is precipitated by hydrolysis. This material is then calcined at 1000-1300 ° C.

Out EP-A-1285031 For example, particles having an opalescent effect are known which have a particle size in the range of 5 μm to 5000 μm, the particles of monodisperse spheres having a diameter of 50 nm-2 μm with a standard deviation of less than 5% in a three-dimensional, densely packed domain-wise and regularly arranged structure mechanically stabilized by a physical or chemical modification. Described is further a process for the preparation of particles in which in a step a) monodisperse spheres with a diameter of 50 nm to 2 microns are suspended in a liquid medium at a standard deviation of less than 5%, b) the suspension on a surface is applied, and c) the liquid medium is removed. The stabilization can be achieved by the following physical and chemical measures. The surface of the balls is modified to achieve cross-linking of the balls or better adhesion of the balls to one another during the formation of the opal structure. For suspension of the spheres in a liquid medium, a compound which is hydrolyzable in water may preferably be added, the hydrolysis product of which precipitates on the spheres during the formation of the opal structure and brings about a chemical bonding of the spheres to one another. In the case of silica spheres, tetraethylorthosilicate is preferably added to the suspension at temperatures of from 50 to 80 ° C., which hydrolyzes to silica and leads to a chemical bonding of the spheres to one another. Alternatively, silicon tetrachloride can be used to treat the coated surface. Also by the addition of soluble silicates, for example sodium water glass and / or polymerizable soluble aluminum compounds in the suspension, the particles according to the invention can be chemically stabilized. Stabilization can also be achieved by treating the coated surface with soluble silicates. Likewise, the particles can be physically stabilized by being embedded in transparent plastics or suitable lacquers. It is essential for the potting material that it is transparent and has a suitable refractive index, which leads to an optimal refractive index difference. For easy processing of the embedding material, such as a paint, it is particularly advantageous if it is low viscosity and its volume during curing is not or only very slightly changed. In one possible embodiment, the embedding material or its precursor is already contained in the suspension in a corresponding volume fraction. In another embodiment of solidifying the opal structure, the surface of the spheres is modified with silanes, which are then crosslinked together during formation of the opal structure by heat or UV radiation. This crosslinking also leads to a solidification of the opal structure. The silanization of monodisperse silica spheres is in DE 4316 814 described in more detail.

In the EP-A-0 955 323 For example, core / shell particles whose core and shell materials can form a two-phase system and which are characterized in that the shell material is filmable and the cores are substantially dimensionally stable under the conditions of filming the shell are not or only greatly enhanced by the shell material are swellable to a small extent and have a monodisperse size distribution, wherein a difference between the refractive indices of the core material and the shell material of at least 0.001. Furthermore, the preparation of the core / shell particles and their use for the production of moldings is described. The method for producing a shaped body comprises the following steps: application of the core / shell particles to a substrate of low adhesiveness, if appropriate, allowing evaporation or stripping of the solvent or diluent possibly contained in the applied layer, transfer of the shell material of the core / shell Particles in a liquid, soft or viscoelastic matrix phase, orientation of the cores of the core / shell particles at least to domains of regular structure, hardening of the shell material for fixing the regular core structure, detachment of the cured film from the substrate and if a pigment or a powder is to be prepared, comminution of the detached film to the desired particle size. In these in the EP-A-0 955 323 revealed core-shell particles "floats" the core in the shell matrix; A distant order of the nuclei is not formed in the melt, but only a close ordering of the nuclei in domains. As a result, these particles are suitable only to a limited extent for processing with methods customary in polymers.

From the patent application WO 03/25035 Moldings are known which consist essentially of core-shell particles whose shell forms a matrix and the core is substantially solid and has a substantially monodisperse size distribution, wherein the jacket is preferably connected via an intermediate layer fixed to the core. In this case, the refractive indices of the core material and the cladding material differ, as a result of which said optical effect, preferably an opalescence, is produced. According to the patent application DE 10204338 In contrast, contrast materials, such as pigments, can be introduced into shaped bodies of such core-shell particles. The incorporated contrast materials cause an increase in brilliance, contrast and depth of the observed color effects in these moldings. The processing of such shaped bodies into pigments is likewise described. In this case, the preparation of the pigments can be carried out, for example, by first producing a film from the core-shell particles, which can optionally be cured. Subsequently, the film can be comminuted in a suitable manner by cutting or breaking and possibly subsequent grinding to pigments of suitable size. This process can be done for example in a continuous belt process.

at These are known from the prior art diffractive colorants usually films, broken films or shaped objects which contain a three-dimensional arrangement of monodisperse spheres. The structure of the diffraction grating requires partially very long Times or complex procedures that use one complicate in large-scale technical applications. Desirable It would be therefore, if methods were available, which allow such diffraction gratings with opaline effect over a large area to create.

One The present invention is therefore a method for Production of coatings with opalartigem effect in the one Dispersion of diffractive Farbmittelprecursoren is applied flat.

In preferred embodiments, the application can thereby using common methods, such as knife coating, spraying, printing or brushing, with doctoring and spraying being the particular preferred application methods.

• – 1 bis 80 Gew.-% Beugungsfarbmittelprecursoren,
• – 1 bis 50 Gew.-% Bindemittel,
• – 10 bis 98 Gew.-% Lösungsmittel,
• – ggf. weitere Hilfsmittel.

A further subject of the present invention is a dispersion of diffraction colorant precursors suitable for the corresponding processing

• From 1 to 80% by weight of diffractive colorant precursors,
• 1 to 50% by weight of binder,
• From 10 to 98% by weight of solvent,
• - If necessary, further aids.

invention Diffraction colorant precursors are usually spherical Particles having a substantially monodisperse size distribution. Preferred particles have an average particle diameter in the Range from about 5 nm to about 2000 nm. It can be about mere spheres of a multiple Marterialien, which possibly be arranged like a shell, in the following also Called cores, or around surface-coated cores up towards core-shell particles with polymeric shell.

there it may be particularly preferred if the cores have a middle Particle diameter in the range of about 5 to 20 nm, preferably 5 to 10 nm. In this case, the cores can referred to as "quantum dots"; they show the corresponding effects known from the literature. To achieve Of color effects in the range of visible light, it is of particular Advantage, if the cores have a mean particle diameter in the range of about 40-500 nm. Preference is given to particles in the Range of 80-500 nm, especially in the range of 200 used to 300 nm, as for particles in this order of magnitude the reflections of different wavelengths of the visible Light clearly different from each other and so for the optical effects in the visible range particularly important opalescence particularly pronounced in different colors occurs. However, it is also in a variant of the present invention preferably, many times this preferred particle size then to reflections corresponding to the higher Orders and thus lead to a broad play of colors.

According to the invention, an opal-like effect is understood as meaning both effects in the visible wavelength range of the light and, for example, effects in the UV or infrared range. Recently, it has become common to call such effects generally photonic effects. All of these effects are optical or opalescent effects in the sense of the present invention, wherein in a preferred embodiment the effect is an opalescence in the visible range. In the sense of a customary definition of the term, the diffraction colorants obtained according to the invention are photonic crystals (cf. News from chemistry; 49 (9) September 2001; Pp. 1018-1025 ).

According to the invention, it may be preferred if the core consists of a material which either does not flow or becomes fluid at a temperature above the flow temperature of the jacket material. This can be achieved by the use of polymeric materials having a correspondingly high glass transition temperature (T _g ), preferably crosslinked polymers or by using inorganic core materials.

It in a variant of the invention particularly preferred when the core from organic polymers, which are preferably crosslinked.

In another likewise preferred variant of the invention consists of Core of inorganic materials, preferably metals or semi-metals or metal chalcogenides or metal pnictides. As chalcogenide are referred to in the context of the present invention, such compounds, in which an element of the 16th group of the periodic table of the electronegative Binding partner; as Pnictide those in which an element of 15. Group of the periodic table of the electronegative binding partners is.

preferred Cores consist of metal chalcogenides, preferably metal oxides, or metal pnictides, preferably nitrides or phosphides. Metal in terms of these terms are all elements that are in the Comparison to the counterions as an electropositive partner can, like the classical metals of the subgroups respectively the main group metals of the first and second main groups as well but also all elements of the third main group, as well as silicon, Germanium, tin, lead, phosphorus, arsenic, antimony and bismuth. To the preferred metal chalcogenides and metal pnictides especially silica, alumina, zirconia, iron oxides, Titanium dioxide, ceria, gallium nitride, boron and aluminum nitride, Silicon and phosphonitride or mixtures thereof.

As a starting material in a variant of the present invention preferably monodisperse cores of silica are used, for example, after the in US 4,911,903 can be obtained described method. The cores are produced by hydrolytic polycondensation of tetraalkoxysilanes in an aqueous ammonia medium, wherein first a sol of primary particles is produced and then brought by a continuous, controlled metered addition of tetraalkoxysilane, the resulting SiO ₂ particles to the desired particle size. With this method, monodisperse SiO ₂ cores with average particle diameters between 0.05 and 10 μm can be produced with a standard deviation of 5%.

Furthermore, SiO ₂ cores are preferred as the starting material, with (half) metals or non-absorbing metal oxides, such as. As TiO ₂ , ZrO ₂ , ZnO ₂ , SnO ₂ or Al ₂ O ₃ , are coated. The preparation of SiO ₂ cores coated with metal oxides is described, for example, in US Pat US 5,846,310 . DE 198 42 134 and DE 199 29 109 described in more detail.

Also suitable as starting material are monodisperse cores of non-absorbing metal oxides, such as TiO ₂ , ZrO ₂ , ZnO ₂ , SnO ₂ or Al ₂ O ₃ or metal oxide mixtures. Their production is for example in EP 0 644 914 described. Furthermore, the method is according to EP 0 216 278 for the production of monodisperse SiO ₂ cores easily and with the same result transferable to other oxides. To a mixture of alcohol, water and ammonia, whose temperature is adjusted with a thermostat to 30 to 40 ° C, are added with intensive mixing tetraethoxysilane, tetrabutoxy, Tetrapropoxyzirkon or mixtures thereof in one pour and the resulting mixture for another 20 seconds intensively stirred, forming a suspension of monodisperse cores in the nanometer range. After a post-reaction time of 1 to 2 hours, the cores in the usual manner, for. B. by centrifuging, separated, washed and dried.

Farther are as starting material and monodisperse cores made of polymers suitable, the particles, for example metal oxides included contain. Such materials are, for example, from the company micro caps development and sales GmbH in Rostock. According to customer requirements microencapsulation based on polyesters, polyamides and natural and modified carbohydrates.

It is also possible to use monodisperse cores of metal oxides which are coated with organic materials, for example silanes. The monodisperse cores are dispersed in alcohols and modified with common organoalkoxysilanes. The silanization of spherical oxide particles is also in DE 43 16 814 described.

The cores may also contain dyes. For example, so-called nanocolorants, such as those in WO 99/40123 are described used. The revelation of WO 99/40123 is hereby expressly included in the disclosure of the present application.

When particularly suitable for the production of laminar coatings have also been core-shell particles whose coat with connected to the core via an intermediate layer. In a preferred embodiment consists of the shell of these core-shell particles from organic polymers, which preferably have at least one partially crosslinked intermediate layer are grafted onto the core. It is essential according to the invention that a refractive index difference consists of the mantle and the core under the processing conditions stays firm.

in the Regard to the possibility of the invention relevant Properties of the cores, in particular of the invention Core-shell particles vary as needed, it may be appropriate be that the cores one or more polymers and / or copolymers (Core polymers) or that they consist of such polymers. Preferably, the cores contain a single polymer or copolymer. For the same reason, it is appropriate that also the shell of the core-shell particles according to the invention one or more polymers and / or copolymers (shell polymers; Matrix polymers) or polymer precursors and, if appropriate, auxiliary and additives, the composition of the Coat can be chosen so that they are non-swelling Environment at room temperature substantially dimensionally stable and is tack-free.

With the use of polymer substances as shell material and possibly Nuclear material gains the expert the freedom of their relevant properties, such as B. their composition, the particle size, the mechanical Data, the refractive index, the glass transition temperature, the melting point and weight ratio of core: shell and thus also the performance properties of the core / shell particles ultimately determine the characteristics of it impacted diffractive colorant.

Polymers and / or copolymers which may or may not be included in the core material are high molecular compounds which conform to the specification given above for the core material. Suitable polymers are both polymers and copolymers of polymerizable unsaturated monomers and polycondensates and copolycondensates of monomers having at least two reactive groups, such as. As high molecular weight aliphatic, aliphatic / aromatic or wholly aromatic polyester, polyamides, polycarbonates, polyureas and polyurethanes, but also aminoplast and phenolic resins, such as. Mela min / formaldehyde, urea / formaldehyde and phenol / formaldehyde condensates.

to Production of epoxy resins which are also suitable as core material are usually epoxide prepolymers, for example, by reaction of bisphenol A or other bisphenols, Resorein, hydroquinone, hexanediol or other aromatic or aliphatic di- or polyols or phenol-formaldehyde condensates or mixtures thereof with each other with epichlorohydrin or others Di- or polyepoxides are obtained, with further for condensation competent compounds directly or in solution mixed and allowed to cure.

Conveniently, the polymers of the core material are crosslinked in a preferred variant of the invention (Co) polymers, since these are usually only at high temperatures show their glass transition. These crosslinked polymers can either already in the course of the polymerization or polycondensation or Be crosslinked copolymerization or copolycondensation or they can be completed after the actual (co-) polymerization or (co) polycondensation in a separate process step postcrosslinked.

For the jacket material is suitable, as for the core material, in principle, polymers of the classes already mentioned above, provided they be selected or built so that they are the above for the sheath polymers given specification.

polymers that meet the specifications for a jacket material, are also found in the groups of polymers and copolymers polymerizable unsaturated monomer as well as the Polycondensates and copolycondensates of monomers containing at least two reactive groups, such as. As the high molecular weight aliphatic, aliphatic / aromatic or wholly aromatic polyesters and polyamides.

Under Considering the above conditions for the Properties of the shell polymers (= matrix polymers) are for their production in principle selected building blocks from all Suitable groups of organic film formers. Especially if the matrix of the diffractive colorant of crosslinked organic polymers should be formed, the selection of shell polymers can be almost arbitrarily. It just has to be ensured that these polymers can be provided with crosslinkable groups.

Some other examples like the wide range of illustrate the preparation of the sheath suitable polymers.

Should the coat be comparatively low breaking, so are suitable For example, polymers such as polyethylene, polypropylene, polyethylene oxide, Polyacrylates, polymethacrylates, polybutadiene, polymethylmethacrylate, Polytetrafluoroethylene, polyoxymethylene, polyesters, polyamides, polyepoxides, Polyurethane, rubber, polyacrylonitrile and polyisoprene.

Should the coat be relatively high refractive, so are suitable for the jacket, for example, polymers with preferably aromatic Basic structure such as polystyrene, polystyrene copolymers such. Eg SAN, aromatic-aliphatic polyesters and polyamides, aromatic polysulfones and polyketones, polyvinyl chloride, polyvinylidene chloride and suitable selection of a high refractive index core material also polyacrylonitrile or polyurethane.

In a particularly preferred embodiment according to the invention of core-shell particles, the core is crosslinked polystyrene and the sheath of a polyacrylate, preferably polyethyl acrylate and / or Polymethylmethacrylat, which is mixed with crosslinkable monomers.

in the Regarding the processability of the core-shell particles to diffraction colorants it is beneficial if the weight ratio of core to coat in the range of 2: 1 to 1: 5, preferably in the range of 3: 2 to 1: 3, and more preferably in the range of 1: 1 to 2: 3 lies. Generally it applies here that it is advantageous the jacket portion increase as the particle diameter of the cores increases.

The Core-shell particles which can be used according to the invention can be produced by different methods. A preferred Possibility to get the particles is a procedure for the production of core-shell particles, by a) surface treatment monodisperse cores, and b) applying the shell of organic Polymers on the treated cores.

In a process variant, the monodisperse cores in a step a1) by emulsions obtained polymerization.

In a preferred variant of the invention, a crosslinked polymeric intermediate layer is applied to the cores in step a), preferably by emulsion polymerization or by ATR polymerization, which preferably has reactive centers to which the shell can be covalently attached. ATR polymerization here stands for Atomic Transfer Radicalic Polymerization, as used, for example, in K. Matyjaszewski, Practical Atom Transfer Radical Polymerization, Polym. Mater. Sci. Closely. 2001, 84 is described. The encapsulation of inorganic materials by ATRP is described, for example, in US Pat T. Werne, TE Patten, Atomic Transfer Radical Polymerization from Nanoparticles: A Tool for the Preparation of Well-Defined Hybrid Nanostructures and for Understanding the Chemistry of Controlled / "Living" Radical Polymerization from Surfaces, J. Am. Chem. Soc. 2001, 123, 7497-7505 and WO 00/11043 described. The implementation of this method as well as the performance of emulsion polymerizations are familiar to those skilled in the polymer production and described for example in the above-mentioned references.

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, it is responsible for rapid and complete curing the paint film, on the other hand, it determines, for. B. in reaction coatings, 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.

commercial Binders are never pure chemical compounds, but technical Products. By introducing hydrophilic or reactive groups or by their blocking, by esterification, etherification, copolymerization or mixture with other polymers, binders are synthesized, in solvent-based paints, water-based paints, UV-curing Systems or powder coatings can be processed and the respective requirements for the coating materials and the correspond to coatings produced from them.

Common biomaterials 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), polymethyl methacrylate, polypropylene, polystyrene, polytetrafluoroethylene, polyurethane, polyurethane / tar combination, polyvinyl acetate, polyvinyl butyral, polyvinyl chloride, Chlorinated polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, chlorinated rubber, cyclo rubber, butadiene-based elastomer polystyrene, silicone polymer, saturated polyester, tar, formaldehyde-urea resin and unsaturated polyester.

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 Alkyldiphenyloxiddisulfonate 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 one or more acrylic or methacrylic groups are attached. 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.

Sie werden bevorzugt in Grundierungen eingesetzt und liefern harteLackie rungen mit gutem Stand und guter Chemikalienbeständigkeit. Die freie Hydroxy-Gruppe bewirkt verbesserte Pigmentbenetzung und gute Haftung auf dem Substrat.Epoxy acrylates are the reaction product of bisphenol A and acrylic acid.

They are preferably used in primers and provide hard coatings with good stability and good chemical resistance. The free hydroxy group causes improved pigment wetting and good adhesion to the substrate.

Urethane acrylates are obtained by reacting hydroxyacrylates with diisocyanates. You own for varnishing flexible substrates and for open-pore varnishes. The compounds based on aromatic isocyanates tend to yellowing in contrast to the aliphatic.

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.

Further it may be in the dispersions of the invention also trade in nail polishes. Typical to the invention Use of suitable nail varnishes consist essentially of solutions Suspensions or emulsions of certain substances. It is here in particular the binders, such as nitrocellulose or various Synthetic resins, in particular polyacrylates, polymethacrylates, toluenesulfonamide-formaldehyde resins, Toluene sulfonamide-epoxy resins, alkyd resins or polyvinyl acetate to call. Further, nail varnishes usually contain suitable ones Solvents for the binders, usually Solvent mixtures are used. Typical solvents In addition to water, 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. soluble Be offset dyes. In addition, in the mixture plasticizer (such as camphor or dibutyl phthalate) and by-products (eg, toluene or xylene). These Nail varnishes harden by evaporation of the solvent as well the other volatiles depending on the layer thickness of the paint, the temperature and the type of Solvent. Next to that is the curing time still of other influences (eg air inflow) dependent.

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, for example polyurethane resins, acrylic resins, alkyd resins, epoxy resins or melamine resins. In this case, the resin is preferably selected so that it is water-soluble, appears white or transparent in the water, inexpensive and easy to is as non-flammable as possible and is not toxic or hyperallergenic. It can be further essential that the paint is fast-drying and has good film-forming properties at temperatures above 10 ° C.

critical for the intensity of the observed effects also the difference of refractive indices of nuclei and matrix of Coating. Inventive coatings preferably have a difference between the refractive indices of the core material and the matrix material of at least 0.001, preferably at least 0.01 and more preferably at least 0.1 on. Should the coatings of the invention show technically exploitable photonic effects, so are refractive index differences of at least 1.5 is preferred. The appropriate selection of nuclear materials and binders prepares the expert in this case no difficulties and can, for example, with the help of popular tables to refractive indices of materials.

In a particular embodiment of the invention, the Dispersion in addition to the diffraction colorant precursors further nanoparticles contain. These particles will be in terms of their particle size so selected that they are in the cavities of the spherical packing fit from the cores and so change the arrangement of the cores little. By targeted selection of appropriate materials and / or the particle size is on the one hand possible the optical effects of the diffractive colorants to change, for example, the intensity too increase. On the other hand, by storage suitable "Quantum dots "the matrix will be functionalized accordingly. Preferred materials are inorganic nanoparticles, in particular Nanoparticles of metals or II-VI or III-V semiconductors or of materials that have the magnetic properties of the materials influence. Examples of preferred nanoparticles are Gold, zinc sulfide, hematite or gallium arsenide.

In a likewise preferred embodiment of the present invention Invention contain the dispersions as auxiliaries at least a contrast material. The contrast materials cause an increase brilliance, contrast and depth of observed color effects the coatings of the invention. Under contrast materials are inventively all materials understood that such a reinforcement of the optical effect cause. These are usually contrast materials around pigments.

For the purposes of the present invention, pigments are understood to mean any solid substance which exhibits an optical effect in the visible wavelength range of the light. According to the invention, in particular those substances are referred to as pigments that follow the definition of pigments DIN 55943 respectively. DIN 55945 correspond. According to this definition, a pigment is a practically insoluble in application medium, inorganic or organic, colored or achromatic colorant. In this case, both inorganic and organic pigments can be used according to the invention.

According to their physical mode of operation, pigments can be classified into absorption pigments and luster pigments. Absorption pigments are those pigments which absorb at least part of the visible light and therefore cause a color impression and in extreme cases appear black. Luster pigments are after DIN 55943 respectively DIN 55944 those pigments in which caused by directional reflection on predominantly flat trained and aligned metallic or high-refractive pigment particles gloss effects. According to these standards, interference pigments are described as luster pigments whose coloring effect is wholly or predominantly based on the phenomenon of interference. These are in particular so-called mother-of-pearl pigments or fire-colored metal bronzes. Of particular economic importance among the interference pigments are the pearlescent pigments, which consist of colorless, transparent and highly refractive platelets. After orientation in a matrix, they produced a soft gloss effect called pearlescent. Examples of Peilglanzpigmente are guanine-containing fish silver, pigments based on lead carbonates, bismuth oxychloride or titanium dioxide mica. In particular, the titanium dioxide mica, which are characterized by mechanical, chemical and thermal stability, are often used for decorative purposes.

Both absorption and gloss pigments can be used according to the invention, it also being possible to use interference pigments in particular. It has been shown that the use of absorption pigments is particularly preferred for increasing the intensity of the optical effects. Both white and color or black pigments can be used, the term color pigments meaning all pigments which give a different color impression than white or black, for example Heliogen ^™ Blue K 6850 (from BASF, Cu phthalocyanine pigment) , Heliogen ^™ Green K 8730 (BASF, Cu phthalocyanine pigment), Bayferrox ^™ 105 M (Bayer, iron oxide-based red pigment) or chrome oxide green GN-M (Bayer, chromium oxide-based green pigment). Due to the color effects achieved, the black pigments are again preferred among the absorption pigments. For example, here are pigmentary Carbon black (eg the carbon black product line from Degussa (in particular Purex ^TM IS 35 or Corax ^™ N 115)) and iron oxide black, manganese black and cobalt black and antimony black. Black mica grades can also advantageously be employed as black pigment (for example, Iriodin ^TM 600, Merck;.. Iron oxide-coated mica).

It It has been shown that it is invented by Advantage is when the particle size of the at least one Contrast material is at least twice as large as the Particle size of the core material. Are the particles of the contrast material smaller, so are only insufficient optical Achieved effects. It is believed that smaller particles, the Ausordnung the cores in the matrix interfere and a change cause the forming grid. The invention preferred used particles of at least twice the size of Cores interact only locally with the grid formed from the core. Electron micrographs prove that the embedded Particles do not disturb the grid of core particles or only slightly disturb them. It is with the particle size of the contrast materials, often also platelet-shaped as pigments are, in each case the largest extent of the particles meant. When platelet-shaped pigments have a thickness have in the range of the particle size of the cores and or even below that, it disturbs the grating orders according to available investigations not. It has also been shown that the shape of the stored contrast material particles no or has little effect on the optical effect. It can according to the invention both spherical and also platy and acicular Contrast materials are stored. Of importance only seems the absolute particle size in proportion to be the particle size of the nuclei. Therefore, it is preferred according to the invention when the particle size the at least one contrast material is at least twice as large as the particle size of the core material, wherein the particle size of the at least one contrast material preferably at least four times as large as the particle size of the nuclear material, since then the observable interactions still are lower.

A reasonable upper limit of the particle size of the contrast materials results from the boundary at which the individual particles themselves become visible or due to their particle size affect the mechanical properties of the diffractive colorant. The determination of this upper limit prepares the expert no Difficulties.

From Meaning for the invention desired Effect is also the amount of contrast material that is used. It has been shown that effects are common observed when at least 0.05% by weight of contrast material, be used as based on the weight of the dispersion. Especially it is preferred if the dispersion is at least 0.2% by weight and particularly preferably contains at least 1% by weight of contrast material, because these increased levels of contrast material according to the invention in usually lead to more intense effects.

Vice versa affect larger amounts of contrast material possibly the processing properties of the cores and thus complicate the preparation of inventive Coatings. In addition, it is expected that above a certain proportion of contrast material, that of the respective Material depends, the formation of the grid of cores is disturbed and rather oriented contrast material layers form. Therefore, it is preferred according to the invention if the dispersion contains a maximum of 20% by weight of contrast material, it being particularly preferred if the dispersion is at most 12 Wt .-% and particularly preferably at most 5 wt .-% contrast material contains.

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 taken from the Rowe Color Index, 3rd Edition, Society of Dyers and Colourists, Bradford, England, 1971. 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-hydroxy-pyrazolone-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) triphenyl-carbinol 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-methyl-fuchsonimmonium 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 black :1 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.

Further advantageous examples are the following pearlescent pigment types based on mica / Me talloxid: 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 rotviolett 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.

The Dyes and pigments can be used individually as well be present in a mixture and be mutually coated with each other, wherein by 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.

According to the invention preferred Dispersions are characterized in that the total amount of or the diffractive colorant precursors in the range of 2% by weight to 50 wt .-%, based on the total weight of the dispersion selected becomes.

In In a further variant of the invention, it may be preferred if the Weight ratio of binder to diffraction colorant precursors in the dispersion is less than 3 to 7. It can further preferred dispersions 10 to 30% by weight of diffractive colorant precursors, 20 to 50% by weight of binder, 30 to 50% by weight of solvent contain.

One Another object of the present invention is a method for the preparation of a dispersion for surface application, characterized in that at least one diffractive colorant precursor with at least one suitable carrier and at least one Binder, and optionally other ingredients mixed becomes. The dispersions of the invention can In doing so, they are manufactured using techniques that are familiar to those skilled in the art well known.

Even without further statements, it is assumed that a person skilled in the art can make the most of the above description. The preferred embodiments are therefore to be construed as merely descriptive and not in any way limiting disclosure. The complete disclosure of all applications and publications cited above and below are incorporated by reference into this application. The following examples are intended to illustrate the present invention. However, they are by no means to be considered limiting. All compounds or components included in the Zu can be used, are either known and commercially available or can be synthesized by known methods.

Examples

ALMA

Allylmethacrylat

AN

Acrylnitril

APS

Ammoniumperoxodisulfat

BDDA

Butan-1,4-dioldiacrylat

CHMA

Cyclohexylmethacrylat

MMA

Methylmethacrylat

SDS

Dodecylsulfat Natriumsalz

SDTH

Natriumdithionit

PCHMA

Poly(cyclohexylmethacrylat)

PS

Poly(Styrol)

Used abbreviations:

ALMA

allyl methacrylate

AT

acrylonitrile

APS

ammonium

BDDA

Butane-1,4-diol diacrylate

CHMA

cyclohexyl

MMA

methyl methacrylate

SDS

Dodecyl sulfate sodium salt

SDTH

sodium

PCHMA

Poly (cyclohexyl methacrylate)

PS

Poly (styrene)

Example 1 Preparation of spheres as Beugungsfarbmittelprecursor

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 stirrer is turned off 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 1c: Production of particles with core of polystyrene, intermediate layer of p (MMA-co-ALMA) and sheath from poly (cyclohexyl methacrylate)

In a preheated to 75 ° C 1-liter stirred tank reactor with propeller stirrer, argon inert gas inlet and reflux condenser is heated to 4 ° C template, consisting of 217 g of water, 3.6 g of styrene (MERCK, destabilized) and 130 mg of SDS (MERCK) filled and with vigorous stirring dispersed. Immediately after filling the reaction by directly successive addition of 50 mg SDTH (MERCK), 350 mg APS (MERCK) and again 50 mg SDTH, each in 5 g water solved, started. After 20 minutes, a monomer emulsion from 8.1 g of BDDA (MERCK, destabilized), 72.9 g of styrene (Fa. MERCK, destabilized), 0.375 g SDS, 0.1 g KOH and 110 g water a period of 120 min continuously dosed. The reactor contents is stirred for 30 minutes without further addition. After that takes place an addition of 200 mg of APS dissolved in 5 g of water. To another 60 minutes stirring is a second monomer emulsion from 1.5 g of ALMA (MERCK, destabilized), 13.5 g of MMA (MERCK), destabilized), 0.075 g SDS and 20 g water over one Period of 25 min continuously dosed. The reactor contents is then stirred for 30 minutes without further addition. Thereafter, 200 mg of APS are added, dissolved in 5 g of water. It is then a monomer emulsion 120 g of CHMA (from Degussa, destabilized), 120 g of water and 0.4 g SDS continuously metered over a period of 150 min. The almost complete reaction of the monomers is subsequently stirred for another 60 minutes. The core-shell particles subsequently become precipitated in 1 l of methanol, the precipitation by Add 25 g of concentrated aqueous saline completes the suspension with 1 L of dist. Added water, sucked off and dried.

Example 1d: Preparation of particles with poly (methyl methacrylate) core and polystyrene jacket

In a preheated to 75 ° C 1-liter stirred tank reactor with propeller stirrer, argon inert gas inlet and reflux condenser is heated to 4 ° C template, consisting of 217 g of water, 0.4 g of ALMA (MERCK, destabilized), 3.6 g of MMA (Fa. MERCK, destabilized) and 23 mg SDS (MERCK) and dispersed with vigorous stirring. Immediately after filling the reaction is initiated by the direct addition of 30 mg SDTH (MERCK), 150 mg APS (MERCK) and again 30 mg SDTH, each dissolved in 5 g of water, started. After 20 min a monomer emulsion of 9.6 g ALMA (Merck, destabilized), 96 g MMA (MERCK, destabilized), 0.35 g SDS, 0.1 g KOH and 130 g of water over a period of 120 min continuously added. The reactor contents are stirred for 60 minutes without further addition. Thereafter, an addition of 100 mg APS, dissolved in 5 g of water. After stirring for a further 10 minutes, a second Monomer emulsion of 120 g of styrene (MERCK, destabilized), 0.4 g SDS and 120 g of water over a period of 150 min continuously added. For almost complete Abreaktion the monomer is then stirred for a further 60 min. The core-shell particles are then dissolved in 1 liter of methanol precipitated, the precipitation by addition of 25 g completed concentrated aqueous saline, the suspension with 1 L of dist. Water added, filtered off with suction and dried.

Example 2:

An aqueous dispersion of the particles from Example 1a-d having 30% by weight of particle content and 4.5% by weight of Triton ^™ X405 (octylphenol ethoxylate having an average number of repeating units of ethylene oxide, commercial product of The Dow Chemical Company). is poured into the open frame of a hand doctor blade (wet film thickness about 200 microns) and applied to a black cardboard at a take-off speed of about 1 cm / s.

in the The case of example 2a and 2b shows a weak opal effect. Examples 2c and 2d give films with a clear after drying Opal effect.

Example 3:

In each case one dispersion of the particles from Example 1c-d with 20% by weight of particle content and 4% by weight of Triton ^™ X405 (octylphenol ethoxylate having an average number of repeating units of ethylene oxide, commercial product of The Dow Chemical Company) in acetone cast into the open frame of a hand doctor blade (wet film thickness approx. 200 μm) and applied to a black cardboard at a take-off speed of approx. 1 cm / s. After drying, the films show a distinct opal effect.

Example 4:

A dispersion of SiO ₂ particles according to Example 1a is stabilized with 5% by weight of a methoxypropoxyacetate / butyl acetate block copolymer (Disperbyk 182, Altana) in butyl acrylate and poured into the open frame of a hand doctor blade (wet film thickness about 200 μm ) and applied to a black cardboard at a take-off speed of approx. 1 cm / s.

Content of SiO ₂ (wt.%): Example 4a 5% by weight Example 4b 10% by weight Example 4c 15% by weight Example 4d 20% by weight Example 4e 25% by weight

The resulting films show an opal effect in the green-blue area.

Example 5: Mirror varnish

Component A:

• 3.7 g Bayhydur BL5130 (Bayer)
• 7.3 g of CMCAB 641-0.2 dispersion (Eastman)
• 8.2 g of tripropylene glycol monomethyl ether (Dowanol TPM, Dow)

Component B:

• 19 g of water
• 0.3 g of dimethylamine

Component C:

• 60 g of a dispersion of particles according to Example 1c or 1d in water (32% by weight solids content)
• 0.4 g tego Foamex 822 (from Tego)
• 3.4 g of hydropalate 1080 (Cognis)

component A is mixed with stirring, then becomes Component B added dropwise. After 390 min residence time, the predispersed Component C was added.

Of the Paint is applied by means of spiral blade or by spraying. To 5 minutes airing, the paint is 45 min at 90 ° C. hardened. It shows an angle-dependent Color effect on the sample plates.

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

• US 4703020 [0006]
• - EP 1285031 A [0007]
• - DE 4316814 [0007, 0025]
• EP 0955323 A [0008, 0008]
• WO 03/25035 [0009]
• - DE 10204338 [0009]
• US 4911903 [0021]
• US 5846310 [0022]
• - DE 19842134 [0022]
• - DE 19929109 [0022]
• - EP 0644914 [0023]
• - EP 0216278 [0023]
• WO 99/40123 [0026, 0026]
• WO 00/11043 [0043]

Cited non-patent literature

• - news from chemistry; 49 (9) September 2001; Pp. 1018-1025 [0016]
• K. Matyjaszewski, Practical Atom Transfer Radical Polymerization, Polym. Mater. Sci. Closely. 2001, 84 [0043]
• - T. Werne, TE Patten, Atomic Transfer Radical Polymerization from Nanoparticles: A Tool for the Preparation of Well-Defined Hybrid Nanostructures and for Understanding the Chemistry of Controlled / "Living" Radical Polymerization from Surfaces, J. Am. Chem. Soc. 2001, 123, 7497-7505 [0043]
• - DIN 55943 [0072]
• - DIN 55945 [0072]
• - DIN 55943 [0073]
• - DIN 55944 [0073]

Claims (14)

Process for producing coatings with opaline effect in which a dispersion of diffraction colorant precursors is applied flat. Method according to claim 1, characterized in that the application is done by doctoring or spraying. Containing dispersion i. From 1 to 80% by weight of diffractive colorant precursors, ii. From 1 to 50% by weight of binder, iii. 10 to 98% by weight of solvent, iv. if necessary further aids. A method according to any one of claim 1 or 2 or dispersion according to claim 3, characterized in that the diffractive colorant precursors spherical particles with a substantially monodisperse size distribution are. Process or dispersion according to at least one of preceding claims, characterized in that the spherical particles consisting essentially of an organic Polymer, which is preferably crosslinked exist. Process or dispersion according to at least one of preceding claims, characterized in that the spherical particles of inorganic materials, preferably Metals or semi-metals or metal chalcogenides or metal pnictides in particular silica, alumina, zirconia, Iron oxides, titanium dioxide, ceria, gallium nitride, boron and aluminum nitride and silicon and phosphorus nitride or mixtures thereof as core material are preferred. Process or dispersion according to at least one of preceding claims, characterized in that the spherical particles consist essentially of polymers, contain the particles, for example metal oxides included. Process or dispersion according to at least one of preceding claims, characterized in that the Diffraction colorant precursors in the optical Properties consist essentially of core-shell particles, whose mantle forms a matrix and whose core is essentially fixed is and a substantially monodisperse size distribution wherein a difference between the refractive indices of Core material and the jacket material. Process or dispersion according to at least one of preceding claims, characterized in that the mean diameter of the spherical particles in the area of about 50-500 nm, preferably in the range of 80-500 nm and most preferably in the range of 200 to 300 nm. Dispersion according to at least one of the preceding Claims, characterized in that the total amount of the diffractive colorant precursor (s) from the range of 2 % By weight to 50% by weight, based on the total weight of the dispersion, is selected. Dispersion according to at least one of the preceding Claims, characterized in that the weight ratio from binder to diffractive colorant precursors less than 3 to 7 is. Dispersion according to at least one of the preceding Claims, characterized in that the dispersion contains at least one dye or pigment, wherein the preparation preferably at least one effect pigment, in particular contains a pearlescent pigment. Dispersion according to at least one of the preceding Claims, characterized in that the dispersion i. From 10 to 30% by weight of diffractive colorant precursors, ii. 20 to 50% by weight of binder, iii. From 30 to 50% by weight of solvent, iv. if necessary further aids. Process for the preparation of a dispersion for planar Application, characterized in that at least one diffractive colorant precursor with at least one suitable carrier and at least one binder, and optionally other ingredients is mixed.