WO1998049243A1 - Effect multiphase organic colouring agent, and production of same - Google Patents

Abstract

The present invention pertains to an effect organic colouring agent from a multiphase mixture containing at least two organic substances, with one or more dispersed phases, jointly specified as phase 1, and with a continuous matrix phase (phase 2), characterized as follows: the dispersed phase (phase 1) does not swell in the matrix phase (phase 2) or, if any, in a very low proportion; there is a difference between the refractive indexes of phases 1 and 2. The invention also relates to the method for producing such effect colouring agents as well as the necessary solid, pasty or fluid preparations from phase 1 monodispersed polymers contained in a substance mixture which is liquid at a normal temperature or becoms liquid only at a higher temperature and which contains phase 2 polymer precursors to be converted into phase 2 polymers, and/or dispersed phase 2 polymers, as well as known monodispersed polymers. The invention further relates to the use of said effect colouring agents or the above-mentioned preparations used in the production of decorative and/or protective coatings, printing lacquers and inks involving said effect colouring agents.

Description

 Organic multi-phase effect colorant, its production and its use.

The present invention relates to an organic effect colorant consisting of a multiphase mixture of at least two organic substances, with one or more disperse phases, hereinafter referred to collectively as phase 1, and a continuous matrix phase (phase 2), the disperse phase (phase 1) in the matrix phase (phase 2) does not swell, phase 1 in phase 2 forms at least domains of regular structure and there is a difference between the refractive indices of phases 1 and 2. The invention further relates to the production of these effect colorants, preparations suitable for their production and monodisperse polymers, the use of the effect colorants according to the invention or the preparations mentioned for the production of decorative and / or protective coatings and the production of lacquers, printing inks and inks using the effect colorants according to the invention.

Effect colorants are colorants that change the color impression, the brightness and / or the reflectivity when the viewing direction (the viewing angle) is varied. As a rule, they have a platelet-shaped structure, ie the thickness of the pigment particles is significantly less than their lateral extent. Known examples of effect colorants are aluminum flakes or the pigments which are commercially available under the names ^® Mica, ^® Iriodin or ^® Paliochrom. Metal effect pigments, eg aluminum flakes, produce a mirror effect when viewed vertically; when viewed from the side, this does not appear. It is therefore a chiaroscuro Observe effect. The same appearance can also be found in the mica effect pigments based on mica.

Iriodin and paliochrome pigments also show enhanced interference effects and self-absorption. In addition to the light-dark effect, a weak color change can also be observed with them when the viewing angle changes. (Literature: Dr. U. Zorll, "Pearlescent Pigments", Vinantz Verlag, ISBN 3-87870-429-1).

From US-A-4, 434, 010 pigments are known based on inorganic, which have pronounced color flops. These pigments are characterized by an extremely homogeneous structure consisting of layers with different refractive indices. This structure leads to pronounced interference effects, which are used for color generation. However, the production of these pigments is difficult and only possible using complex and costly production processes.

Organic effect pigments based on cholesteric liquids are known from US Pat. No. 5,364,557. In these, an interference effect results from a helical superstructure. Here, too, the materials required for production are complicated to manufacture and therefore very expensive. The pigments are produced from the cholesteric liquid crystals (LCs) in such a way that the cholesteric mass is applied in a thin layer to a carrier film, photochemical polymerization is carried out in the LC phase, and the film thus obtained is detached from the film and ground . In addition to the expensive production of the starting materials, it is a very serious disadvantage of this method that during the production process the greatest attention must be paid to the orientation of the LCs, since even the smallest impurities can negatively influence them. A method for coating and printing substrates, in which cholesteric liquid crystals are used, is known from WO 96/02597. In this process, one or more liquid-crystalline compounds, at least one of which is chiral and which have one or two polymerizable groups, are applied to a substrate together with suitable comonomers - if this is done by a printing process, dispersants are also added to the mixture - and copolymerized. If they are brittle, the layers obtained in this way can be detached from the substrate, comminuted and used as pigments.

Aqueous, monodisperse polymer dispersions are also known, e.g. from T. Okubu, Prog. Polym. Be. 18 (1993) 481 to 517 and W. Luck, H. Wesslau, Festschrift Carl Wurstler, BASF 1960, C.A.:55:14009d, which, in liquid form, tend to show pronounced latex crystallization after cleaning, and thus lead to color effects.

A large number of publications are known for producing monodisperse particles, e.g. EP-A-0 639 590 (preparation by precipitation polymerization), A. Rudin, J. Polym. Sci., A: Polym. Be. 33 (1995) 1849 to 1857 (monodisperse particles with a core-shell structure), EP-A-0 292 261 (production with the addition of seed particles).

EP-A-0 441 559 describes core-shell polymers with different refractive indices of the layers and their use as additives for paper coating compositions.

Heat-controlled optical switching elements have recently become known (SCIENCE, Vol. 274, (1996), pages 959 to 960), in which the temperature dependence of the particle size of poly- (N-isopropylacrylamide) dispersions or the volume / temperature relationship of poly- (N-iso- propylacrylamide) gels is used. A first embodiment of these switches consists of an aqueous poly (N-isopropylacrylamide) dispersion, the particles of which are arranged in a lattice shape and are substantially higher below the phase transition temperature than above it. The consequence of this is that the absorbance rises sharply at about 530 nm in the temperature range between 10 and 40 ° C. The system thus acts as an optical switch and limiter.

In a second embodiment, highly charged polystyrene particles, which form a space lattice, are embedded in a poly (N-isopropylacrylamide) hydrogel. When the temperature changes, the volume of the hydrogel changes and with it the lattice spacing of the polystyrene particles. The result is that when the temperature changes from approx. 10 to approx. 40 ° C., the position of the absorption maximum shifts from approx. 700 to approx. 460 nm. This system can be used as a tunable optical filter. These materials are naturally not suitable for use as colorants or pigments.

The object of the present invention was to provide new organic effect colorants which can be produced inexpensively from readily accessible starting materials by a process with low susceptibility to interference. They should be stable, in particular they should have no swellability in organic and aqueous media.

This object is achieved by the effect colorants according to the invention.

The invention thus relates to an organic multiphase effect colorant consisting of a mixture of at least two organic substances which form a multiphase system, the multiphase system a) one or more solid disperse phases, hereinafter collectively referred to as phase 1, and b) a solid continuous matrix phase (phase 2) and c) if appropriate, auxiliaries and / or additives are contained in the matrix phase, which is characterized in that that the disperse phase (phase 1) cannot be swelled by the matrix phase (phase 2) or swells to a very small extent, phase 1 in phase 2 forms at least domains of regular structure and there is a difference between the refractive indices of phases 1 and 2.

For the purposes of the present invention, a matrix is a medium which connects and fixes the particles of the disperse phase to one another. The matrix does not necessarily have to completely fill the entire space between the particles of the disperse phase, but it suffices if it forms adhesive points in the area of the contact points of the core particles, by means of which these are fixed in a regular arrangement. Depending on the proportion of the matrix material, the matrix will more or less completely fill the space between the particles of the disperse phase. In analogy to continuous phases of disperse systems, a matrix defined in the sense of the present invention can also be regarded as a continuous phase.

The characteristic "low swellability" of the phase 1 polymer particles in phase 2 means that the average diameter of the phase 1 particles increases by at most 10% of the original value when the particles are embedded in the matrix phase and the latter has dried.

The effect colorant according to the invention generally contains 20 to 99% by weight, preferably 40 to 95% by weight, in particular 60 to 90% by weight of the dispersed phase 1 polymers, and 1 to 80% by weight, preferably 5 to 60% by weight, in particular 10 to 40% by weight, constituents of phase 2, phase 2 in turn 60 to 100% by weight , preferably 70 to 99% by weight, in particular 80 to 95% by weight of polymer material, and 0 to 40% by weight, preferably 1 to 30% by weight, in particular 5 to 20% by weight of auxiliary and / or contains additives.

The effect colorant according to the invention preferably consists of the constituents indicated above in the stated proportions. The sum of the percentages given for individual components of a reference mixture (e.g. "effect colorant" or "phase 2") is 100% for each individual reference mixture.

The difference Δn in the refractive index between phases 1 and 2 is of essential importance. It is at least 0.001, preferably at least 0.01, in particular at least 0.1 units. The disperse phase 1 can have the higher, the matrix phase (phase 2) the lower refractive index or vice versa. The first case is preferred.

It is particularly advantageous if the disperse phase (phase 1) not only swells as little as possible in phase 2 itself, but also in solutions, dispersions or melts or in liquid precursors thereof.

The particles of the disperse phase have a particle size of 0.05 to 5 μm, preferably 0.1 to 2 μm, in particular 0.15 to 1.0 μm. Particles with a particle size of 0.2 to 0.7 μm are particularly preferred for the disperse phase. The phase 1 polymers are preferably in a monodisperse distribution, ie a narrow particle size distribution. The particle size distribution is characterized by the polydispersity index PI, which is defined by the following formula:

PI = (D ₉₀ - D ₁₀ ) / D ₅₀

In this formula, D ₉₀ , D ₅₀ and D _{10 denote} the particle diameters in which the integral of the distribution function dG = f (D) * dD, where G is the polymer mass, D the particle diameter, the values 0.9 (= 90 wt. -%), 0.5 (= 50% by weight) or 0.1 (= 10% by weight) of the total mass of the polymer substance.

The attached figure illustrates this connection. It shows in a coordinate system, on the abscissa the particle sizes (D) and on the ordinate the mass fractions (G) of the particles of a given size, the dashed curve of the distribution function of the particle sizes of a polymer dispersion. Furthermore, in the same coordinate system it shows the solid curve of the integral of the distribution function, on which the points for 10, 50 and

90% mass fraction and the associated points D ₁₀ , D ₅₀ and D _{90 of} the particle diameter are marked by crosses.

As the particle size distribution becomes narrower, the PI value approaches zero, the wider the polydisperse the particle size distribution, the larger the PI. The particle size distribution can be determined in a manner known per se, for example with the aid of an analytical ultracentrifuge (see, for example, W. Mächtle, Makromol. Chem. 185 (1984), pp. 1025 to 1039) or according to the present application with a commercial CHDF device, and are calculated from the PI values obtained. For the Polymer particles suitable for the present invention have PI values below 0.6, preferably below 0.4, in particular below 0.3.

The polymer particles of the disperse phase 1 have an essentially spherical, preferably spherical, shape. They form macroscopic domains of crystal-like structure in the matrix phase. In many cases, the particles in this structure arrange themselves in a tight spherical packing.

The disperse phase (phase 1) contains or consists of one or more polymers and / or copolymers. Polymers and copolymers in the sense of this description of the invention are high-molecular compounds which correspond to the specification given above. Both polymers and copolymers of polymerizable unsaturated monomers are suitable, as are polycondensates and copolycondensates of monomers with at least two reactive groups, e.g. High molecular weight aliphatic, aliphatic / aromatic or fully aromatic polyesters, polyamides, polycarbonates, polyureas and polyurethanes, but also aminoplast and phenoplast resins, such as melamine / formaldehyde, urea / formaldehyde and phenol / formaldehyde condensates.

The phase 1 polymers are expediently crosslinked (co) polymers, since these best meet the requirement for low swellability. These crosslinked polymers can either have already been crosslinked in the course of the polymerization or polycondensation or copolymerization or copolycondensation, or they can have been postcrosslinked in a separate process step after the actual (co) polymerization or (co) polycondensation has been completed . A detailed description of the chemical composition of suitable polymers follows below. For various applications of the effect colorants according to the invention, it is expedient and desirable if the matrix phase (phase 2) also contains or consists of one or more polymers and / or copolymers. For the matrix phase, as for phase 1, polymers of the classes already mentioned are suitable in principle, provided that they are selected or constructed in such a way that they correspond to the specification given above for phase 2 polymers. This means that they must have a refractive index that differs significantly from the phase 1 polymers, ie that when using a high-index polymer phase 1, a low-index polymer phase 2 must be used and vice versa. Furthermore, they should not tend to swell or dissolve the particles of the phase 1 polymers.

A further requirement of the phase 2 polymers is that they can be converted into a liquid preparation either by undecomposed melting or by dissolving in a solvent or dispersion, or that they can be prepared from precursors in a layer of a liquid or pasty preparation (Prepolymers, monomers).

However, for many applications of the effect colorants according to the invention, it is expedient and desirable if the matrix phase (phase 2) also contains or consists of a polymer material which, after the formation of the continuous matrix, ie after film formation, has a low solubility or swellability in organic solvents and / or water. For particularly valuable applications of the effect colorants according to the invention, for example for the production of highly stable pigments or protective coatings, it is therefore preferred to also crosslink the polymers of the matrix phase (phase 2). This crosslinking can take place via the same polyfunctional monomers as with the phase 1 polymers, taking into account the required refractive differences.

For certain applications, such as for the production of coatings or color foils, it is advantageous if the polymer material of the matrix phase is an elastically deformable polymer, e.g. consists essentially of natural rubber or a synthetic rubber. In this case it can be achieved that the color of a layer of the colorant according to the invention varies with stretching and compression. Also of interest for use are layers of effect colorants according to the invention which show dichroism.

Polymers that meet these specifications can also be found in the groups of polymers and copolymers of polymerizable unsaturated monomers and also in the polycondensates and copolycondensates of monomers with at least two reactive groups, for example the high molecular weight aliphatic, aliphatic / aromatic or fully aromatic polyesters and polyamides, but also the aminoplast and phenoplast resins, such as the melamine / formaldehyde urea / formaldehyde and phenol / formaldehyde condensates, which condense further on drying with strong crosslinking. The same applies analogously to epoxy resins consisting, for example, of mixtures of polyepoxides and polyamines or polyols, which solidify to form resin-like masses on drying. Epoxy resins are usually used to prepare epoxy prepolymers, for example by reaction of bisphenol A or other bisphenols, such as resorcinol, hydroquinone, hexanediol, or other aromatic or aliphatic diols or polyols or phenol-formaldehyde condensates or mixtures thereof with epichlorohydrin, dicyclopentadiene. diepoxid or other di- or polyepoxides are obtained, with further for condensation qualified compounds mixed directly or in solution and allowed to harden.

Taking into account the above conditions for the properties of the phase 2 polymers, in principle selected building blocks from all groups of organic film formers are suitable for their production.

Matrix polymers which are soluble in organic solvents and which are therefore advantageously used as film formers for matrices which bind by drying are, for example, modified or not too high molecular weight polyesters, cellulose esters such as cellulose acetobutyrate, polyurethanes, silicones, polyether- or polyester-modified silicones.

Some other examples may illustrate the wide range of suitable phase 2 polymers.

Case 1: Disperse phase high refractive index, matrix low refractive index: hydrogels, i.e. water-swollen polymers such as polyacrylamide gels, polyacrylic acid gels, or cellulose gels, MF, UF and PF resins, drying and film-forming polymer dispersions, polymers such as polyethylene, polypropylene, polyethylene oxide, polyacrylates, polymethacrylates, polybutadiene, polymethyl methacrylate, polytetrafluoroethylene, polytetrafluoroethylene, polytetrafluoroethylene , Polyamides, polyepoxides, polyurethane, rubber, polyacrylonitrile and polyisoprene.

Case 2: Disperse phase low refractive index, matrix high refractive index:

Polymers with a preferably aromatic basic structure such as polystyrene, polystyrene copolymers such as SAN, aromatic-aliphatic polyesters and polyamides, aromatic polysulfones and polyketones, PF resins, polyvinyl chloride, polyvinylidene chloride and, if a suitable phase 1 is selected, also MF resins, polyacrylonitrile or Polyurethane. The auxiliaries and / or additives optionally contained in the matrix phase are used to set the application data or properties desired or required for use and processing. Examples of such auxiliaries and / or additives are leveling agents, adhesives, release agents, plasticizers, application aids, agents for viscosity modification,

Film-forming aids, fillers, coloring additives, for example organic dyes or organic or inorganic pigments which are soluble in water or organic media, and, if appropriate, residues of organic or inorganic solvents, dispersants or diluents which, for example, determine the "open time" of the formulation, i.e. extend the time available for their application on substrates, waxes or hot melt adhesive.

If desired, stabilizers against UV radiation and weather influences can also be added to the polymers, in particular the phase mixture. For this, e.g. Derivatives of 2,4-dihydroxybenzophenone, derivatives of 2-cyano-3,3'-diphenyl acrylate, derivatives of 2,2 ', 4,4'-tetrahydroxybenzophenone, derivatives of o-hydroxyphenyl-benzotriazole, salicylic acid esters, o -Hydroxyphenyl-s-triazine or sterically hindered amines. These substances can also be used individually or as mixtures.

The effect colorants according to the invention show very interesting color effects which are dependent on the angle of incidence of light and / or the viewing angle and which are presumably caused by interference on the spatial lattice formed by the phase 1 polymer particles. The angle-dependent color change is particularly impressive if the effect dye according to the invention is applied to a dark, for example black, background, ie to a non-selectively absorbing substrate. Dye additives give the effect colorants according to the invention their own color, which is superimposed by the interference effect.

The effect colorants according to the invention can be in the form of solid pieces of any size, e.g. in the form of three-dimensional moldings, such as plastics, apparatus parts, tubes, rods of various cross-sections, strands, fibers, chips or powders, in the form of decorative or protective layers, in the form of films, or in the form of pigments. Of course, the forms mentioned can also be in a mixture with solid or liquid additives such as solvents, dispersants, diluents, auxiliaries or extenders.

In a preferred embodiment of the present invention, the effect colorant according to the invention is present as a pigment with a polymer matrix which is resistant to aqueous and organic media. The pigment particles according to the invention have a platelet-shaped structure, i.e. that their thickness is significantly less than their lateral extent. The thickness of pigment particles according to the invention is expediently 1 to 1000 μm, preferably 1 to 100 μm, in particular 10 to 100 μm. The lateral extent is 5 to 5000 μm, preferably 20 to 3000 μm, in particular 50 to 1000 μm. They are obtained, for example, by comminuting a flat film of a mixture of phase 1 and matrix phase 2 using known methods. The beds according to the invention obtained in this way can be used as pigment particles. The pigments according to the invention are surprisingly distinguished by very good light fastness.

In another preferred embodiment, the effect colorant according to the invention lies as a decorative and / or protective coating on one Substrate before. Suitable substrates are, for example, paper, cardboard, leather, foils, cellophane, textiles, plastics, glass, ceramics or metals.

Another object of the present invention are pasty and fluid, in particular spreadable, sprayable or pourable preparations of solid phase 1 polymers of the type described above and specification in a melt, dispersion or emulsion of the phase 2 polymers or in one Normal temperature or only at elevated temperature liquid substance mixture which can be converted into the phase polymers described above on the basis of a content of polymer precursors, namely monomers or prepolymers. For the purposes of this invention, prepolymers are polymers of low or medium degree of polymerization which can be converted into the phase 2 polymers by further condensation or crosslinking. The viscosity of the mass should be so low or by simple measures, for example by gentle heating or by ultrasound, that it can be reduced to such an extent that the phase 1 polymers can at least form domains of a regular arrangement.

Because of the various principally known possibilities for obtaining the phase 2 polymers, the composition of the pasty or liquid substance mixture can be varied in different directions. It can contain or consist of a mixture of the monomers described in more detail below, which have been selected according to their type and proportion so that their (co) polymerization and, if appropriate, crosslinking give the desired phase 2 polymer. The monomers can also be replaced in whole or in part by prepolymers or finished, possibly even crosslinked, phase 2 polymers (film formers) which are dissolved or as a dispersion or emulsion in the remaining monomer mixture or in an inert solution, diluent or Dispersants, for example in an organic solvent or in water, are present. The mi Schung can also contain crosslinking agents, which may be activated by special measures, for example thermally by heating, photochemically by irradiation with actinic electromagnetic radiation, by adding radical or cationic initiators or - in the case of crosslinking agents which act via a condensation or addition reaction - by means of reaction accelerators can be.

If the phase 2 polymer is already in the liquid mixture in the finished form or as a prepolymer in a dispersion, care must be taken to ensure that its polymer particles are so small that they can easily fall into between the particles of phase 1. Polymer-formed interstices and voids can store, or that the phase 2 (pre) polymer particles are deformed under the conditions of solidification of the liquid mixture on the substrate to the extent that a matrix is formed, or that the formation of Domains regular arrangement of phase 1 polymer particles is not hindered. Of course, the same condition also applies to dispersions of prepolymers and precondensates, e.g. for low to medium molecular weight polymers, aqueous thermoset precondensates, for example melamine / formaldehyde precondensates, oligomeric polyesters or polyamides.

The fluid or pasty preparations according to the invention of the effect colorants or of precursors of the effect colorants contain or consist of 20 to 99% by weight, preferably 30 to 90% by weight, in particular 40 to 80% by weight, of the dispersed phase 1 polymers, and 1 to 80% by weight, preferably 10 to 70% by weight, in particular 20 to 60% by weight, of a fluid or pasty mixture of substances, which in turn 5 to 95% by weight, preferably 10 to 90% by weight , in particular 20 to 70% by weight of melted or dispersed phase 2 polymers or polymer precursors, and 95 to 5% by weight, preferably 90 to 10% by weight, in particular 80 to 30 % By weight of solvents, dispersants, auxiliaries and / or additives.

A particularly preferred case is when both the phase 1 and phase 2 polymer are used in the form of polymer dispersions, advantageously in the same dispersant, the phase 2 polymer being film-forming. Because of the same dispersant and the low viscosity of the dispersions, the mixing of the phases is particularly easy in this case.

The transfer of the liquid substance mixture into the solid phase 2, referred to in this description as solidification, depends on the type of preparation and can be carried out routinely. In the simplest case, when the liquid phase is a melt of the phase 2 polymers, the conversion into the solid phase is carried out simply by cooling the melt. If the liquid substance mixture does not already contain the finished phase 2 polymer, this is generated from the monomers by polymerization or condensation and, if appropriate, simultaneous or subsequent crosslinking, or from the prepolymers by further polymerization, further condensation and / or simultaneous or subsequent crosslinking.

If the liquid mixture contains solvents, diluents or dispersants, these are usually evaporated. This can take place before or after any polymerization, condensation, further polymerization or further condensation of precursors and crosslinking which may be necessary to produce the phase 2 polymer. In general, removing the solvent before producing the phase 2 polymer has technical advantages. The liquid substance mixture in which the phase 1 particles are dispersed preferably constitutes a dispersion of the phase 2 polymers in one Dispersant, preferably in water. In this case, the matrix is formed by the confluence of the phase 2 polymer particles which occurs when the dispersant is removed

Prepolymers in the sense of this description are also e.g. Polymers or polycondensates that already have the required length of the base chain, but which are still to be crosslinked.

The crosslinking is carried out using known crosslinking agents described in more detail below.

The (co) polymerization, further polymerization, (co) condensation, further condensation or crosslinking required for curing phase 2 can take place thermally or photochemically, depending on the type of prepolymer. When using free-radically or cationically polymerizable monomers and / or prepolymers, known initiator systems adapted to the processing and curing conditions are to be added. Monomers or prepolymers which harden by condensation or addition reactions do not require such initiators, but, if appropriate, known reaction accelerators. For example, organic peroxides in combination with heavy metal activators can be used as radical initiator systems. Suitable condensation accelerators are e.g. Proton or Lewis acids.

The present invention further provides solid preparations of the phase 1 polymers which, in addition to the phase 1 polymers, contain the amount of phase 2 polymers in powder form required for forming a continuous matrix or a corresponding amount of a mixture of substances which is solid at normal temperature, which can be converted into the phase 2 polymers described above. With the exception of the solvents, diluents or dispersants described above, the solid substance mixture contained in these preparations contains all substances of the pasty or fluid preparations of the phase 1 polymers described above. Examples of these are wax particles or hot melt adhesive. The solid preparations according to the invention of the phase 1 polymers can be converted into the fluid or pasty preparations described above by melting or by adding solvents, diluents or dispersants.

The solid preparations of the effect colorants according to the invention preferably contain or consist of 20 to 99% by weight, preferably 40 to 95% by weight, in particular 60 to 90% by weight of the phase 1 polymers, and 1 to 80% by weight. %, preferably 5 to 60% by weight, in particular 10 to 40% by weight of a solid substance mixture, which in turn 60 to 100% by weight, preferably 70 to 99% by weight, in particular 80 to 95% by weight contains meltable, dispersible or soluble phase 2 polymers or polymer precursors, and 0 to 40% by weight, preferably 1 to 30% by weight, in particular 5 to 20% by weight of auxiliaries and / or additives consists.

For the purposes of this invention, preparations are not only mixtures which can be prepared by mixing the substances contained therein in a prefabricated form, but also mixtures which are obtained as a result of chemical reactions, in particular polymerization reactions. The pasty or fluid preparations described above can be prepared, for example, by prefabricating particles from phase 1 polymers with monomers or prepolymers of phase 2 polymers and, if desired, auxiliaries and / or additives in a liquid dispersant in a separate process step. or diluent are homogenized and the polymer precursors polymerized on or out become. Here, "polymerization" is understood to mean the polymerization of low-molecular building blocks of phase 2 polymers to form higher molecular weight prepolymers, and "polymerization" to mean the polymerization of the polymer precursors to give the finished phase 2 polymers. Those paste-like or fluid preparations which contain finished phase 2 polymers in addition to the phase 1 polymers are particularly preferred. According to the above information, these are obtained by polymerization of the monomers and prepolymers contained in the original mixture to give phase 2 polymers.

Alternatively, in a so-called one-pot process, the phase 1 polymers can first be prepared in a liquid dispersant and / or diluent by one of the abovementioned processes and then, without their isolation, the polymerization or polycondensation batch used to prepare the phase 2 Suitable polymers are added to suitable monomers and their polymerization condensation and / or crosslinking are carried out completely or to the degree of prepolymers, and / or prepolymers suitable for the preparation of the phase 2 polymers can also be added to the batch and their polymerization condensation and / or crosslinking completed become. In addition, further auxiliaries and additives can, if desired, also be added to the batch before or after the polymerization of the phase 2 polymer precursors. Because of the simplicity of execution, this method is preferred for the production of the pasty or fluid preparations according to the invention.

The processes mentioned for the preparation of the pasty or fluid preparations can also advantageously be used for the production of the solid preparations according to the invention by removing the liquid dispersant or diluent from the batch after the preparation of the pasty or fluid preparation described. This can be carried out by any known method. It is particularly preferred to subject the batches to spray drying.

For the implementation of the invention, materials, preferably polymer materials, are required for the disperse phase and the matrix phase, which materials differ significantly in terms of their refractive index, which consequently selectively either a relatively high or a relatively low one

Refractive index have been set. In addition, the above-mentioned requirements for chemical resistance and physical behavior must be set: no or as little mutual penetration of the phases (i.e. no or as little swelling as possible), no chemical

Reactions with the ingredients of the colorants according to the invention and

Environmental components; in particular the phase 2 polymers are said to be prior to

Formation of the matrix have good solubility or dispersibility, but should be inert if possible after matrix formation.

Such polymers can be prepared in a manner known per se by polymerization, polycondensation or polyaddition of polymerizable and / or copolymerizable or (co) condensable or monomers capable of polyaddition reactions, or by higher polymerization or postcondensation or crosslinking of polymeric or oligomeric compounds.

The preparation of the polymers for phase 1 and phase 2 is not restricted to a specific process. Rather, the known methods for polymer production can be used. It is only necessary to distribute the phase 1 polymer, which can be obtained by any process, in a continuous matrix phase, which can also be obtained by any process, in a disperse and regular manner. The methods of emulsion polymerization, suspension polymerization, microemulsion polymerization are preferably employed. tion, or microsuspension polymerization, which use radical polymerization. They have the advantage of not being sensitive to moisture.

Polymerization initiators which decompose either thermally or photochemically, form radicals and thus trigger the polymerization are suitable for triggering the polymerization. Among the thermally activatable polymerization initiators, preference is given to those which decompose between 20 and 180 ° C., in particular between 50 and 80 ° C. In principle, all known photoinitiators and their mixtures can be used for photochemical curing. Examples of suitable photoinitiators are benzophenone and its derivatives, such as alkylbenzophenones, halogen-methylated benzophenones, 4,4'-bis (dimethylamino) benzophenone, benzoin and benzoin ethers such as ethylbenzoin ether, benzil ketals such as benzil dimethyl ketal, acetophenone derivatives such as hydroxy-2 -methyl-l-phenylpropan-l-one or hydroxycyclohexyl phenyl ketone. Acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, for example, are also very suitable. Those initiators which do not have a yellowing effect are preferred.

Particularly preferred polymerization initiators are peroxides such as dibenzoyl peroxide, di-tert-butyl peroxide, peresters, percarbonates, perketals, hydroperoxides, but also inorganic peroxides such as H ₂ O ₂ , salts of peroxosulfuric acid and peroxodisulfuric acid, azo compounds, and boralkyl compounds and homolytically decomposing hydrocarbons. The initiators and / or photoinitiators, which, depending on the requirements of the material to be polymerized, are used in amounts between 0.01 and 15% by weight, based on the polymerizable components, individually or, in order to utilize advantageous synergistic effects, in Combination with each other. For cationic polymerizations, initiators are preferably used which have either Lewis acid character, for example boron trifluoride etherate, aluminum chloride or zinc chloride, or which have charged structures, for example a compound of the formula

optionally in combinations with acylphosphine oxides.

Suitable initiators for anionic polymerization are alkali metal organic compounds, for example methyl lithium, butyllithium, phenyllithium, naphthyllithium, naphthyl sodium, l, 4-disodium-l, l, 4,4-tetrapheπyl-butane or the corresponding lithium compound, diphenylmethyl sodium, di - phenylmethyl potassium, 1-methylstyryllithium or potassium tert-butoxide.

Appropriate processes have also been described for the production of polycondensation products. It is thus possible to disperse the starting materials for the production of polycondensation products in inert liquids and, preferably with low molecular weight reaction products such as water or - e.g. when using dicarboxylic acid di-lower alkyl esters for the production of polyesters or polyamides - lower alkanols.

Polyaddition products are obtained analogously by reacting compounds which have at least two, preferably three, reactive groups such as epoxy, cyanate, isocyanate or isothiocyanate groups with compounds which carry complementary reactive groups. For example, isocyanates react with alcohols to form urethanes, with amines to form urine Substance derivatives, while epoxides react with these complementaries to form hydroxy ethers or hydroxy amines. Like the polycondensation reactions, polyaddition reactions can also advantageously be carried out in an inert solvent or dispersant.

It is also possible to use aromatic, aliphatic or mixed aromatic-aliphatic polymers, e.g. Polyesters, polyurethanes, polyamides, polyureas, polyepoxides or solution polymers, in a dispersant e.g. to disperse or emulsify in water, alcohols, tetrahydrofuran, hydrocarbons (secondary dispersion) and to condense, crosslink and harden in this fine distribution.

Dispersing aids are generally used to prepare the stable dispersions required for these polymerization, polycondensation or polyaddition processes.

Water-soluble, high-molecular organic compounds with polar groups, such as polyvinylpyrrolidone, copolymers of vinyl propionate or acetate and vinypyrrolidone, partially saponified copolymers of an acrylic ester and acrylonitrile, polyvinyl alcohols with different residual acetate contents, cellulose ethers, gelatin, low molecular weight, block copolymers, block copolymers are preferably used as dispersants. polymers containing carbon and / or sulfonic acid groups, or mixtures of these substances. Particularly preferred protective colloids are polyvinyl alcohols with a residual acetate content of less than 35, in particular from 5 to 30 mol% and / or vinylpyrrolidone / vinyl propionate copolymers with a vinyl ester content of less than 35, in particular from 5 to 30% by weight.

Nonionic or ionic emulsifiers, optionally also as a mixture, can be used. Preferred emulsifiers are given if ethoxylated or propoxylated longer-chain alkanols or alkylphenols with different degrees of ethoxylation or propoxylation (eg adducts with 0 to 50 mol of alkylene oxide) or their neutralized, sulfated, sulfonated or phosphated derivatives. Neutralized dialkylsulfosuccinic acid esters or alkyldiphenyloxide disulfonates are also particularly suitable. Combinations of these emulsifiers with the protective colloids mentioned above are particularly advantageous since they give particularly finely divided dispersions.

Methods for the production of monodisperse polymer particles have also already been described in the literature (for example RC Backus, RC Williams, J. Appl. Physics 19, p. 1186, (1948)) and can advantageously be used in particular for the production of the phase 1 polymers become. It is only necessary to ensure that the particle sizes given above are from 0.05 to 5 μm, preferably from 0.1 to 2 μm, in particular from 0.15 to 1.0 μm and especially from 0.2 to 0.7 μm and a polydispersity index of less than 0.6, preferably less than 0.4, in particular less than 0.3, in order to obtain, after the orientation of the particles in phase 2, a grating which exhibits Bragg scattering in the visible, near UV or IR range.

The composition and degree of polymerisation and / or degree of crosslinking are decisive for the required combination of properties, such as chemical and mechanical resistance, physical data.

The resistance of one phase to dissolving or swelling in or through the other phase can be brought about not only by crosslinking the polymers, but also by selecting the monomers for the polymers of the different phases in such a way that "molecularly incompatible" polymers are re receives, ie that - such as oil and water - do not naturally show a tendency to penetrate one another due to different δ _LP values, ie different polarity. The solubility parameters δ _LP characterize the polarity of the compounds in question and have been published for many low molecular weight compounds and polymers (see Brantrup-Immergut, "Polymer Handbook", 3rd edition, J. Wiley, New York, Chapter VII). The greater the difference in δy _? - values between phase 1 and matrix phase 2, the lower the tendency towards molecular mixing or swelling.

By setting the reaction conditions such as temperature, pressure, reaction time, use of suitable catalyst systems, which influence the degree of polymerization in a known manner, and the selection of the monomers used for their preparation according to the type, proportion and mode of addition during the polymerization, the desired combinations of properties of those required can be targeted Adjust polymers.

The light refraction properties of the polymers are also significantly influenced by the selection of the monomers used for their production. Monomers which lead to polymers with a high refractive index are usually those which either have aromatic partial structures or those which have heteroatoms with a high atomic number, such as halogen atoms, in particular bromine or iodine atoms, sulfur or metal ions, i.e. via atoms or groupings of atoms which increase the polarizability of the polymers.

Polymers with a low refractive index are accordingly obtained from monomers or monomer mixtures which do not contain the mentioned partial structures and / or atoms of high atomic number or only contain them in a small proportion. Polycondensates which are suitable for carrying out the present invention are, for example, in particular polyamides, polyesters, polyurethanes or polycarbonates. Of the polyamides, particular mention should be made of polycondensates and cocondensates of aliphatic dicarboxylic acids having 4 to 12 carbon atoms with aliphatic diamines of approximately the same chain length, for example the polyhexamethylene diadipamide (PA 6.6) obtainable from hexamethylenediamine and adipic acid, alicyclic polyamides For example, the product obtainable by condensation of 4,4'-diaminodicyclohexylmethane and decanecarboxylic acid, polycondensates of aminocarboxylic acids, such as polycaprolactam, aromatic or partially aromatic polyamides (“aramids”), such as poly (m-phenylene-isophthalamide) (PMIA ), Poly (m-phenylene terephthalamide) (PMTA). Aramids have a very high chemical and physical resistance and are therefore particularly suitable as phase 1 polymers.

Suitable polyesters consist predominantly, generally to more than 80% by weight, of building blocks which are derived from aromatic dicarboxylic acids and from aliphatic and / or cycloaliphatic diols or from preferably aromatic hydroxycarboxylic acids. Common aromatic dicarboxylic acid building blocks are the divalent residues of benzenedicarboxylic acids, especially terephthalic acid and isophthalic acid; Common diols have 2 to 8 carbon atoms, and those with 2 to 4 carbon atoms are particularly suitable. Common hydroxycarboxylic acids are e.g. p-hydroxybenzoic acid and p- (2-hydroxyethyl) benzoic acid. The aliphatic diol residues can be, for example, all ethylene residues or they can be composed, for example, in a molar ratio of 10: 1 to 1:10 from ethylene and 1,4-dimethylene-cyclohexane residues.

Polyesters in which at least 95 mol% of the

Diol residues are lower alkyl residues with 2 to 4 carbon atoms. Polyester material, for example, which is composed of at least 85 mol% of polyester ethylene terephthalate or polybutylene terephthalate. The remaining 15 mol% then build up from dicarboxylic acid units and diol units which act as so-called modifying agents and which allow the person skilled in the art to specifically influence the physical and chemical properties of phases 1 and 2. Examples of such dicarboxylic acid units are residues of isophthalic acid or of aliphatic dicarboxylic acid such as glutaric acid, adipic acid, sebacic acid; Examples of diol residues with a modifying action are those of longer-chain diols, for example of hexanediol or octanediol, of di- or tri-ethylene glycol or, if present in small amounts, of polyglycol with a molecular weight of about 500 to 2000.

To set certain polyester properties, such as swellability or melt viscosity, it may be desirable to bring about a defined degree of crosslinking. The crosslinking of polymers can take place by reactive, crosslinkable groups which are contained either in the polymer or in its precursors, the prepolymers or monomers, or by subsequently added compounds which contain these reactive groups. If the crosslinking takes place by addition reactions, it is triggered by adding low or high molecular weight compounds which carry groups which are complementary to the reactive groups. Does the polymer e.g. Isocyanate groups or epoxy groups as reactive groups, compounds which carry several OH groups or amino groups, e.g. Diols, polyols or polyesters with a high OH number, for crosslinking. Conversely, of course, polymers which carry OH or amino groups can also be crosslinked by adding low or high molecular weight substances which carry reactive groups.

Compounds which have at least three functional groups capable of ester formation serve as crosslinkers for polyesters. Functional groups capable of ester formation are the OH group, the carboxyl group, Alkoxycarbonyl, especially lower alkoxy-carbonyl, the carboxylic acid anhydride group, and reactive groups derived from these. Examples of common crosslinkers are pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, pyromellitic acid; crosslinking or postcrosslinking can also be carried out by compounds which have at least two, preferably three epoxide, cyanate, isocyanate or isothiocyanate groups.

For the purpose of crosslinking, the polycondensation is carried out in the presence of up to 20% by weight, preferably from 1 to 10% by weight, of the crosslinkers mentioned, or an oligomer (precondensate) or else the polycondensate after the end of the Basic chain structure implemented with appropriate amounts of crosslinkers.

The above-mentioned polyamides, polyureas and polyurethanes can also be crosslinked or pre-crosslinked in an analogous manner to adjust special combinations of properties by using trifunctional or higher functionalized compounds. The crosslinking or the completion of a pre-crosslinking can also be carried out in a separate step following the polycondensation or polyaddition, optionally with the addition of a further reactive component. The polycarbonic acid (derivatives) mentioned for polyesters and polyamino compounds are suitable for crosslinking the polyamides.

The use of polymers and copolymers as polymers is particularly advantageous for the implementation of the present invention, since the wide range of monomers and crosslinking agents available enables the skilled worker to prepare polymers with any required combination of light refraction properties and chemical and physical resistance. An overview of the refractive indices of various common homopolymers and a mathematical formula for calculating the glass transition temperature of copolymers (formula by Gordon and Taylor) can be found, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A21, page 169.

Examples of free-radically polymerizable monomers that lead to polymers with a high refractive index:

Group a): styrene, alkyl-substituted styrenes in the phenyl nucleus, α-methylstyrene, mono- and dichlorostyrene, vinylnaphthalene, isopropenylnaphthalene, isopropenylbiphenyl, vinylpyridine, isopropenylpyridine, vinylcarbazole, vinylanthracene, N-benzy 1-methacrylic acid amide, p-l-methacrylic acid amide .

Group b): acrylates which have aromatic side chains, e.g. Phenyl (meth) acrylate (= abbreviation for the two compounds phenyl acrylate and phenyl methacrylate), phenyl vinyl ether, benzyl (meth) acrylate, benzyl vinyl ether, and compounds of the formulas

In the formulas above and in the form below, for the sake of clarity and simplification of the writing, carbon chains are only represented by the bonds between the carbon atoms. This notation corresponds to the representation of aromatic cyclic compounds, for example the benzene is represented by a hexagon with alternating single and double bonds. Compounds which contain sulfur bridges instead of oxygen bridges are also suitable

In the above formulas, R represents hydrogen or methyl.

The phenyl rings of these monomers can carry further substituents. Such substituents are suitable for modifying the properties of the polymers produced from these monomers within certain limits. They can therefore be used in a targeted manner, in particular to optimize the properties of the effect colorants according to the invention which are relevant in terms of application technology. Suitable substituents are in particular CN, halogen, NO ₂ , alkyl with one to twenty C atoms, alkoxy with one to twenty C atoms, carboxyalkyl with one to twenty C atoms, carbonyalkyl with one to twenty C atoms, or -OCOO -Alkyl with one to twenty carbon atoms in the alkyl chains. The alkyl chains of these radicals can in turn optionally be substituted or interrupted by non-bonded heteroatoms or structural groups such as -O-, -S-, -NH-, -COO-, -OCO- or -OCOO- in non-adjacent positions.

Group c): Monomers which have heteroatoms, such as vinyl chloride, vinylidene chloride, vinylidene bromide, acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylamide and methacrylamide or organometallic compounds such as

Group d): The refractive index of polymers can also be increased by polymerizing in monomers containing carboxylic acid groups and converting the "acidic" polymers thus obtained into the corresponding salts with metals of higher atomic weight, e.g. preferably with K, Ca, Sr, Ba, Zn, Pb, Fe, Ni, Co, Cr, Cu, Mn, Sn or Cd.

The monomers mentioned above, which make a high contribution to the refractive index of the polymers produced therefrom, can be homopolymerized or copolymerized with one another. They can also be copolymerized with a certain proportion of monomers that make a lower contribution to the refractive index. Such copolymerizable monomers with a lower refractive index contribution are, for example, acrylates, methacrylates or vinyl ethers with purely aliphatic radicals.

In preferred embodiments of the present invention, at least the polymers of dispersed phase 1, preferably the polymers of both phases, are crosslinked. In principle, what has been said above for the crosslinking of the polycondensates applies to the crosslinking of the polymers. The crosslinking can take place at the same time as the polymerization, or can be connected to the polymerization in a separate step (postcrosslinking). For various applications of the effect colorants according to the invention, it is advantageous to crosslink the phase 1 polymers already during the polymerization, and to subsequently crosslink the phase 2 polymers.

If corresponding complementary groups are present in the polymer, the abovementioned ones for crosslinking polycondensates can be used. suitable reactive crosslinking agents, such as compounds containing epoxy, cyanate, isocyanate or isothiocyanate groups, can also be used for the crosslinking of polymers.

In addition, all bifunctional or polyfunctional compounds which can be copolymerized with the abovementioned monomers or which can subsequently react with the polymers with crosslinking can also be used as crosslinking agents for polymers.

In the following, examples of suitable crosslinkers are presented, which are divided into groups for systematization:

Group 1: bisacrylates, bismethacrylates, bis-α-chloroacrylates and bisvinyl ethers of aromatic or aliphatic di- or polyhydroxy compounds, in particular of butanediol [butanediol-di (meth) acrylate, butanediol-bis-vinylether], hexanediol [hexanediol-di ( meth) acrylate, hexanediol-bis-vinyl ether], pentaerythritol, hydroquinone, bis-hydroxyphenylmethane, bis-hydroxyphenyl ether, bis-hydroxymethyl-benzene, bisphenol A or with ethylene oxide spacers, propylene oxide spacers or mixed ethylene oxide-propylene oxide spacers. The following formulas illustrate some representatives of this network group:

Other crosslinkers in this group are e.g. Di- or polyvinyl compounds such as divinybenzene or also methylene bisacrylamide, triallyl cyanurate, divinyl ethylene urea, trimethylolpropane tri- (meth) acrylate, trimethylolpropane tri- vinyl ether, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra vinyl ether, and crosslinker with two or more different reactive ends such as (meth) allyl (meth) acrylates of the formulas

wherein R is hydrogen or methyl and n is a number from 1 to 20, preferably from 1 to 10, in particular from 1 to 3. In addition to the illustrated in the above formulas polyether spacers can also polysiloxanes are used as spacers, such as the ^® @ Tegomer® types (manufacturer: Goldschmidt AG).

Group 2: reactive crosslinking agents that have a crosslinking effect, but mostly have a crosslinking effect, for example when heated or dried. Examples include: N-methylol- (meth) acrylamide, acrylamidoglycolic acid and their ethers and / or esters with C _j to C ₆ alcohols, acetacetoxyethyl methacrylamide (AA-EM), diacetone acrylamide (DAAM), glycidyl methacrylate (GMA), Methacryloyloxypropyltrimethoxysilane (MEMO), vinyltrimethoxysilane, m-isopropenylbenzyl isocyanate (TMI).

Group 3: Carboxylic acid groups which have been incorporated into the polymer by copolymerization of unsaturated carboxylic acids are crosslinked like polyvalent metal ions. Acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid are preferably used as unsaturated carboxylic acids for this purpose. Mg, Ca, Sr, Ba, Zn, Pb, Fe, Ni, Co, Cr, Cu, Mn, Sn, Cd are suitable as metal ions. Ca, Mg and Zn are particularly preferred.

Group 4: Post-crosslinking additives. These are bisfunctional or higher functionalized additives which react irreversibly with the polymer (through addition or preferably condensation reactions) to form a network. Examples of these are compounds which have at least two of the following reactive groups per molecule: epoxy, aziridine, isocyanate, acid chloride, carbodiimide or carbonyl groups, furthermore, for example, 3,4-dihydroxy-imidazolinone and its derivatives ( ^® Fixapret @ - Brands of BASF) and blocked polyurethane dispersions. As already explained above, postcrosslinkers with reactive groups such as epoxy and isocyanate groups require complementary reactive groups in the polymer to be crosslinked. For example, isocyanates react with alcohols to form urethanes, with amines to form urea derivatives, while epoxides react with these complementary groups to form hydroxyethers or hydroxyamines. Post-crosslinking is also understood to mean photochemical curing, an oxidative or an air or moisture-induced curing of the systems.

The monomers and crosslinking agents given above can be combined with one another and (co-) polymerized as desired and in such a way that an optionally crosslinked (co-) polymer is obtained with the desired refractive index and the required stability criteria and mechanical properties. It is also possible to use other common monomers, e.g. Additionally copolymerize acrylates, methacrylates, vinyl esters, butadiene, ethylene, propylene, isoprene, for example to adjust the glass transition temperature or the mechanical properties as required.

The present invention also relates to a process for the preparation of the multiphase effect colorant, comprising the following steps: a) Preparation of a suspension of one or more solid, non-swellable phase 1 polymers in a liquid mixture of monomers, prepolymers or polymers of phase 2 , if necessary one

Solvent, diluent in which solids belonging to phase 2 are dispersed or dissolved, and optionally other auxiliaries, the monomer and polymer components being selected such that after the solidification of phase 2 and / or hardening of the phase 2 polymers between phases 1 and 2 there is a difference in the refractive indices b) application of the mixture prepared according to a) to a substrate, c) Orientation of the phase 1 polymer particles to domains of regular structure, d) optionally removing (evaporating or expelling) the solvent or diluent which may be present in the applied layer and e) if necessary curing the film on the substrate, f) detaching the cured film from the substrate g) comminution of the detached film to the desired particle size.

The polymer particles of the disperse phase (phase 1 polymers) can be processed in a separate process step, e.g. be prepared by emulsion, suspension, micro-emulsion or microsuspension polymerization, the process conditions being chosen so that the particle sizes given above are from 0.05 to 5 μm, preferably from 0.1 to 2 μm, in particular 0.15 to 1.0 μm and specifically from 0.2 to 0.7 μm and a polydispersity index PI of less than 0.6, preferably less than 0.4, in particular less than 0.3.

The polymer particles can be isolated from the dispersion obtained. The polymer particles can be isolated by various methods known per se. For example, the liquid phase can be removed from the dispersion by simply allowing it to evaporate or, if necessary, it can be evaporated at elevated temperature and preferably in vacuo, expediently with constant agitation (for example in a rotary evaporator). The method of spray drying is particularly preferred for removing the liquid phase. However, the dispersed particles can also be precipitated by coagulation, filtered off and, if desired, washed and dried. In this way, a powder is obtained which essentially consists of spherical polymer particles of the dimension and size distribution indicated above. This polymer powder is outstandingly suitable for producing the effect colorants according to the invention.

This polymer powder and its use for the production of effect colorants according to the invention are also objects of the present invention.

Alternatively, in a so-called one-pot process after completion of the preparation of the phase 1 polymers by one of the abovementioned processes, without their isolation, the polymerization or polycondensation batch, the monomers suitable for the preparation of the phase 2 polymers can be added and their polymerization, Condensation and / or crosslinking can be carried out completely or to the degree of prepolymers, and / or prepolymers suitable for the preparation of the phase 2 polymers can also be added to the batch and their polymerization, condensation and / or crosslinking can be completed.

In a further advantageous embodiment of pigment production, the mixture is applied in accordance with process step b) to the substrate in the form of a large number of small dots of the desired shape and size. With this method, the comminution step g) is facilitated or can be omitted entirely. The application is expediently carried out by spraying or printing. The shape and size of the dots can be set very precisely by varying the spray or pressure parameters.

The orientation of the polymer particles of phase 1 in the matrix according to step c of the described method according to the invention generally takes place spontaneously. You only have to wait until the desired degree of orientation is reached. However, it is also possible to influence the pre-orientation of the polymer particles in a targeted manner, for example by acceleration, shear or electrostatic or electrodynamic forces on the particles to promote or trigger the formation of the oriented domains. It is also possible to use a substrate which itself has crystalline regions which induce the orientation of the phase 1 polymer particles.

Suitable substrates for carrying out the process according to the invention are solids, on which the cured film of the colorant according to the invention shows only slight adhesion. The low adhesion can be inherent in the substrate or can be brought about by a suitable coating clay or pretreatment with known agents which reduce the adhesion. Examples of suitable substrates are e.g. Glass or hard rubber plates or polyolefin or PTFE plates or foils.

If a flexible, preferably tough, phase 2 polymer is selected, films can also be produced in analogy to the process described above for producing pigments according to the invention. In this case, the hardened layer of the effect colorant according to the invention is separated from the substrate and the comminution is omitted.

For the production of decorative and / or protective coatings, either a) one of the liquid settings of the effect colorants according to the invention described above, or b) a varnish, a printing ink or an ink which - if necessary in addition to other colorants - the effect colorants described above - Pigments crushed film contains, to be coated - optionally pretreated, for example, provided with a primer - to be decorated or protected. All methods known from the prior art are suitable as application methods. For example, the application can be carried out by pouring, dipping, knife coating, brushing, brushing, roll coating, spraying or spraying. In principle, all known printing processes such as screen printing, letterpress printing, flexographic printing, gravure printing, offset printing, pad printing, heat seal printing and other transfer printing methods are also suitable for applying the effect colorant according to the invention. Liquid preparations of the effect dyes according to the invention can also be applied using a ballpoint pen or fountain pen. After application of one of the above-described liquid settings of the effect colorants according to the invention [variant a) the production of decorative and / or protective coatings], the orientation of the phase 1 polymers in the layer, as described above, is waited for or carried out and then the curing of the liquid phase 2 preparation initiated, or [variant b) the production of decorative and / or protective coatings] the paint, the printing ink or the ink dried as usual and optionally cured.

Decorative and / or protective coatings can also be produced from solid, powdery mixtures of phase 1 polymer particles with meltable phase 2 polymers or phase 2 prepolymers according to the invention, by using these powders by a known method for powder coating, for example by electrostatic means , evenly applied to the substrate and melted. The phase 2 (pre-) polymers are kept in the molten or softened state until the orientation of the phase 1 polymer particles and then, when the phase 2 polymers are used themselves, by simple cooling, when the prepolymers are used by higher condensation or Higher polymerization, and if necessary simultaneous or subsequent crosslinking, solidified. Another object of the present invention is the use of the organic effect colorants according to the invention, according to variant b), the production of decorative and / or protective coatings, for coloring in lacquers, printing inks and inks, and for the mass coloring of polymers, as a safety signal color and for production optical filter. Since the interference colors can be set from the infrared to the ultraviolet range, the effect dyes according to the invention can also be used to produce markings and security marks which are invisible to the human eye. These can be found on the basis of the angle dependence of the reflection radiation with detectors of appropriate spectral sensitivity.

The invention also relates to the lacquer mentioned above in the description of variant b) for the production of decorative and / or protective coatings from a solvent-containing, water-based or from a solvent and / or water-free binder and color bodies, which is an organic effect colorant and optionally contains other coloring substances. The lacquer according to the invention preferably contains a binder which cures thermally or photochemically.

Another object of the invention is the printing ink or ink mentioned in the description of variant b) for the production of decorative and / or protective coatings from a solvent-containing, water-based or from a solvent and / or water-free binder and color bodies, which is an organic effect colorant according to the invention contains. The printing ink or ink according to the invention preferably contains a binder which dries thermally or oxidatively or cures photochemically. The following embodiments illustrate the invention. The emulsifiers used in the examples have the following compositions: Emulsifier 1:40% by weight solution of a sodium salt of a C ₁₂ / C ₁₄ paraffin sulfonate emulsifier 1:15% by weight. -% solution of linear sodium dodecylbenzenesulfonate

Emulsifier 3:20 wt. -% solution of linear ammonium dodecylbenzene sulfonate.

The particle size distributions were determined using the capillary hydrodynamic fractionation method. The CHDF 1100 particle size analyzer from Matec Applied Sciences was used. The polydispersity index P.I. calculated according to the formula given above.

Unless otherwise stated, solutions are aqueous solutions.

EXAMPLE 1

A submitted amount of water (465 g) and 6% of the monomer emulsion MEl are heated in a pilot stirrer with anchor stirrer (100 rpm) to 85 ° C. under nitrogen and with 22% of a solution of 4.8 g sodium persulfate in 187 g water (initiator solution) transferred. After 15 min. the remaining monomer emulsion MEl is started in 2 hours and the rest of the initiator solution is fed continuously in 2.25 hours. The batch is then kept at 85 ° C. for a further hour, cooled and 16 g of 10% by weight solutions of tert-butyl hydroperoxide and ascorbic acid are added to each of them. The coagulate and speck-free dispersion obtained has a pH of 4.4, an LD of 52%, a weight-average particle size of 236 nm (light scattering) and a solids content of 39.1%. The Particle size distribution is monodisperse with a maximum at 242 nm and a PI of 0.24 (CHDF). The dispersion is yellowish white and does not tend to crystallize.

Composition of the monomer emulsion ME 1:

384 g of n-butyl acrylate

400 g acrylonitrile

16 g acrylic acid

14 g emulsifier 1

529 g water

EXAMPLE 2

A quantity of water (333 g) and 0.5% of the monomer emulsion ME2 were heated in a pilot stirrer with anchor stirrer (100 rpm) to 80 ° C. under nitrogen and mixed with 70 g of a 2.5% strength by weight aqueous solution of Sodium persulfate (initiator solution) added. After 15 min. the remaining monomer emulsion ME2 and a further 300 g of initiator solution are continuously fed in 4 hours. Thereafter, 0.25% by weight (based on monomer) of hydrogen peroxide is treated and a solution of 5.6 g of mercaptoethanol in 30 g of water is added over the course of an hour. After cooling, the pH of the mixture is adjusted to 6.8 using concentrated ammonia solution. The product is filtered through a 120 μm filter and results in a medium-viscosity, coagulate and speck-free dispersion with an LD value of 24%, a weight-average particle size of 550 nm (light scattering) and a solids content of 60.6%. The particle size distribution is monodisperse with a maximum at 440 nm (CHDF). The polymer dispersion leads to strong wall crystallization when standing in a glass vessel, recognizable by the Formation of magnificent, colored, platelet-shaped, difficult to disrupt crystals.

Composition of ME 2:

1701 g of n-butyl acrylate

91 g acrylonitrile

18 g acrylic acid

122 g N-methylol methacrylamide, 15% by weight 61 g emulsifier 2

270 g water

EXAMPLE 3

A mixture of 840 g of water, 100 g of styrene, 0.5 g of sodium styrene sulfonate and 150 mg of calcium chloride is heated to 80 ° C. in a pilot stirrer with an anchor stirrer (300 rpm) under nitrogen. 25 g of a solution of 2 g of sodium persulfate in 80 g of water are added. After 20 min. the remaining initiator solution is metered in over 4 h and then stirred at 80 ° C. for a further 5.5 h. The product is filtered through a 120 μm filter (4 g coagulate) and gives a speck-free dispersion with an LD value of 1%, a weight-average particle size of 470 nm (light scattering) and a solids content of 8.7%. The dispersion does not tend to crystallize.

EXAMPLE 4A

Example 1 is repeated with the difference that the monomer emulsion contains only 380 g of n-butyl acrylate, but additionally 4 g of 1,4-butanediol diacrylate. The coagulate and speck-free dispersion obtained has a pH 4.3, an LD value of 48%, a weight-average particle size of 245 nm (light scattering) and a solids content of 38.7%. The particle size distribution is monodisperse with a maximum at 258 nm (CHDF). The dispersion is yellowish white and does not tend to crystallize.

EXAMPLE 4B

Example 1 is repeated with the difference that the monomer emulsion contains only 380 g of n-butyl acrylate, but additionally 4 g of allymethacrylate. The coagulate and speck-free dispersion obtained has a pH of 4.4, an LD of 53%, a weight-average particle size of 226 nm (light scattering) and a solids content of 39.0%. The particle size distribution is monodisperse with a maximum at 233 nm (CHDF). The dispersion is yellowish white and does not tend to crystallize.

EXAMPLE 5

A submitted amount of water (465 g) and 5% of the monomer emulsion ME5 were heated in a pilot stirrer with anchor stirrer (100 rpm) to 85 ° C. under nitrogen and, when the internal temperature reached 70 ° C., with 14 g of a 2.5% by weight. solution of sodium persulfate. After 15 min. the remaining monomer emulsion ME5 is started in 2 hours and the rest of the initiator solution continuously in 2.25 hours. The reaction mixture is then kept at 85 ° C. for a further hour, cooled and 16 g of 10% strength by weight solutions of tert-butyl hydroperoxide and ascorbic acid are added to each. The coagulate and speck-free dispersion obtained has a pH of 2.2, the particle size distribution is monodisperse with a maximum at 242 nm (CHDF). The dispersion is yellowish white and does not tend to crystallize. Composition of ME 5:

700 g n-butyl methacrylate 31.5 g emulsifier 3 568 g water

EXAMPLE 6

Example 1 is repeated using monomer emulsion ME6. The coagulate and speck-free dispersion obtained has a pH of 4.4, a weight-average particle size of 227 nm (light scattering) and a solids content of 39.2%. The particle size distribution is monodisperse with a maximum at 242 nm (CHDF). The dispersion is yellowish white and does not tend to crystallize.

Composition of ME 6:

304 g of n-butyl acrylate

400 g methyl methacrylate

80 g butanediol diacrylate

16 g acrylic acid

14 g emulsifier 1

529 g water

EXAMPLE 7

60 g of a sample of the sample diluted to a solids content of 20% by weight

Dispersion from Example 1 are poured onto a rubber plate (size 14 × 14 cm) and left to dry at 25 ° C. After 36 hours, a hard, easily breaking white layer with an average thickness of approx. 1 mm obtained, the surface of which has many small crystalline areas of approximately 1 mm in diameter and thus leads to strong angle-dependent interference.

EXAMPLE 8

Example 7 is carried out analogously with the dispersion from example 2. The filming forms a homogeneous, transparent filming with no visible color effects.

EXAMPLE 9

50 g of the dispersion from Example 1 are mixed with 10 g of the dispersion from Example 2 and 20 g of water and 5 min. touched. The mixture is allowed to dry in a rubber mold (14x14 cm) at 25 ° C. After 24 hours a flexible, white, opaque film with strong surface crystallization has formed. The film shows strong angle-dependent interference phenomena. When tempering (60 min. At 60 ° C) a transparent, yellow polymer matrix is formed.

EXAMPLE 10

25 g of the dispersion from Example 1 are mixed with 5 g of a semi-crystalline polyurethane dispersion having a solids content of about 40% ^(® Luphen D 200 A, BASF AG), 15 min. stirred and allowed to dry in a rubber mold (14x6 cm) at 25 ° C. After 24 hours a flexible, white, opaque film with strong surface crystallization has formed. The film shows strong angle-dependent interference phenomena. EXAMPLE 11

55 g of the dispersion from Example 1 are mixed with 5 g of a partially crystalline polyurethane dispersion with a solids content of about 40% (Luphen D 200 A from BASF AG), 0.15 g of hexamethylene diamine (50% by weight) and 0.1 g of a potassium salt of a perfluorocarboxylic acid with 12 carbon atoms (50% by weight) stirred and spread in a mold (14x14 cm) on aluminum foil and left to dry. After drying, a strongly torn, hard film of about 1 mm thick is obtained, which has an intense angle-dependent interference phenomenon on the surface with a color flop from red to green.

EXAMPLE 12

The mixture of Example 11 is allowed to film on a polyethylene film. The result does not differ from that of Example 11.

EXAMPLE 13

The film from Example 11 is crushed into pieces about 2 × 2 mm in size. A pouring clay is obtained which produces a strong glitter effect and can be used as a pigment.

EXAMPLE 14

50 g of the dispersion from Example 4a are stirred with 1 g of a PEO-PPO block copolymer ( ^® Pluronic PE 6400 from BASF AG) and allowed to film on a 14 × 6 cm rubber plate. After drying, a coherent, flexible film with an intense angle-dependent interference phenomenon on the surface is obtained, which is a color flop from red to green. A similar result is obtained if, instead of the dispersion from Example 4a, the same amount of the dispersion from Example 4b is used.

EXAMPLE 15

30 g of the dispersion from Example 3 are poured out into a rubber mold (14 × 6 cm). After drying, a hard, very easily crumbling film is obtained with very strong signs of interference in the viewing angle of approx. 30 ° in the green area.

EXAMPLE 16

A few drops of the dispersion from Example 1 are dropped onto a polyethylene beaker and allowed to run off. After 1 min. Drying time at room temperature results in a highly iridescent coating clay at the wetted points, which can be rubbed off very easily in the form of a powder.

EXAMPLE 17

A mixture of 50 g of the dispersion from Example 1, 1.6 g of dispersion from Example 2 and 0.8 g of bis (ethylhexyl) sulfosuccinic acid ester (60%) are stirred and added dropwise

a) dripped onto the outer surface of a polyethylene cup and b) onto a sheet of paper

and let it run each time. After 1 min. Drying time in the room temperature is a strongly iridescent coating obtained at the wetted points, which can no longer be rubbed off. EXAMPLE 18

35 of a Expoxidharzes g ^(® Epicote 828 of Messrs. Shell) are dissolved in 60 g of THF, and 10 g of hexamethylenediamine (50 wt .-%) are stirred (= epoxy resin A). 5 g of a (Cg-alkyl) phenol ethoxylate with 25 mol of EO (as a 20% strength by weight solution) are stirred into 30 g of the dispersion from Example 6, and 6 g of the epoxy resin solution A prepared above are then added dropwise. The white dispersion mixture is knife-coated onto a 120 μm thick film which, in the dry state, has intense color changes depending on the viewing angle.

EXAMPLE 19

20 g of the dispersion from Example 6 are mixed with 10 g of the epoxy resin solution A from Example 18 and left to stand in a sealed glass vessel. After 3 days the mass has hardened and lies as an insoluble molded body in the surrounding THF. The molded body has intense, viewing angle-dependent color phenomena on the surface. After removing, placing on an absorbent surface and air drying, a hard polyepoxide block is obtained.

EXAMPLE 20

In each case 30 g of the dispersion from Example 6 are mixed with 3, 6, 9 and 12 g of the epoxy resin solution A from Example 18 with stirring. About 1 g of the mixtures is knife-coated on glass (120 μm film), about 1 g is placed dropwise on a vertically clamped sheet of paper and allowed to run off. The remnants are allowed to dry and harden in rubber molds. The dried films show strong surface color dependencies with a viewing angle and a color flop of green to blue-violet and increasing film hardness with increasing proportions of epoxy resin. The films can be crushed and / or ground.

EXAMPLE 21

In each case, 30 g of the dispersion from Example 6 are mixed with 0, 2, 4 or 8 g of the dispersion from Example 2, with stirring, and the mixtures are allowed to film in glass molds (about 15 × 15 cm). After 36 hours, the films are compared. The results are shown in the following table:

EXAMPLE 22

30 g of the dispersion from Example 4 are allowed to film in a rubber mold. A transparent, hard film is obtained which has no color effects. If, on the other hand, 30 g of the dispersion are mixed with 1.9 g of hydroxyethyl acrylate while stirring and this mixture is allowed to film, after the water has evaporated and the mixture has solidified, an almost transparent, yellow film with intense interference color effects and a color flop of green becomes preserved after blue. After standing in the air for about 12 hours the color effects disappear. The enrichment of the hydroxyethyl acrylate in the edge areas of the dispersion particles creates a refractive index difference between the surface areas and the inside of the particles and therefore leads to strong interference effects on the surface, which disappear again with the evaporation or even distribution of the monomers in the polymer film.

EXAMPLE 23

The mixture from Example 9 is filled into a high-pressure spray gun (Proxon, Gala 500) and sprayed with 3 bar air pressure onto a black lacquered metal, glass or paper surface and air-dried. The spraying process was repeated two more times, resulting in a uniformly covered, uniform surface.

EXAMPLE 24

A mixture of 10 g of the dispersion of Example 6 and 2 g of the dispersion of Example 2 is diluted with 5 g of water and 0.5 g of ethylene glycol. The mixture can be drawn into a print cartridge and written on paper with a fountain pen. After drying in air, a white typeface with color changes from green to blue is obtained on black paper. The writing cannot be rubbed off the paper and cannot be wiped off with a swab soaked in ethanol. After annealing to 80 ° C, the white typeface disappears.

Claims

claims

1. Organic multi-phase effect colorant from a mixture of at least two organic substances which form a multi-phase system, the multi-phase system a) one or more disperse phases, hereinafter referred to collectively as phase 1, and b) a continuous matrix phase (phase 2) and c) if appropriate, auxiliaries and / or additives are present in the matrix phase, characterized in that the disperse phase (phase 1) cannot be swelled by the matrix phase (phase 2) or swells to a very small extent, phase 1 in phase 2 at least Domains regular structure and there is a difference between the refractive indices of phases 1 and 2.

2. Effect colorant according to claim 1, characterized in that the difference Δn between the refractive indices of the

Phases 1 and 2 is at least 0.001, preferably 0.01, in particular 0.1 units.

3. effect colorant according to at least one of claims 1 and 2, characterized in that the disperse phase (phase 1) contains one or more polymers (phase 1 polymers).

4. effect colorant according to at least one of claims 1 to 3, characterized in that the matrix phase (phase 2) contains one or more polymers (phase 2 polymers).

5. effect colorant according to at least one of claims 1 to

4, characterized in that the particles of the disperse phase have a particle size of 0.05 to 5 μm, preferably of 0.1 to 2 μm, in particular of 0.15 to 1.0 μm.

6. Effect colorants according to at least one of claims 1 to

5, characterized in that it is 20 to 99 wt .-%, preferably 40 to 95 wt .-%, in particular 60 to 90 wt .-% of the dispersed phase 1 polymers, and 1 to 80 wt .-%, preferably 5 to 60% by weight, in particular 10 to 40% by weight

% Contains constituents of phase 2, phase 2 in turn comprising 60 to 100% by weight, preferably 70 to 99% by weight, in particular 80 to 95% by weight of polymer material, and 0 to 40% by weight, preferably 1 contains up to 30 wt .-%, in particular 5 to 20 wt .-% auxiliaries and / or additives.

7. effect colorant according to at least one of claims 1 to

6, characterized in that it is present as a pigment with a polymer matrix resistant to aqueous and organic media.

8. effect colorant according to at least one of claims 1 to

7, characterized in that the thickness of the pigment particles is significantly less than their lateral extent.

9. effect colorant according to at least one of claims 1 to

8, characterized in that the thickness of the pigment particles is 1 to 100 microns, in particular 10 to 100 microns, with a lateral extent of 20 to 3000 microns, preferably 50 to 1000 microns.

10. Effect colorant according to at least one of claims 1 to 9, characterized in that it is present as a decorative and / or protective coating, with a polymer matrix resistant to aqueous and organic media.

11. Effect colorant according to at least one of claims 1 to 9, characterized in that it is present as a film with a polymer matrix resistant to aqueous and organic media.

12. Use of the organic effect colorants of claim 1 or 7 for coloring in lacquers, printing inks, inks, for mass coloring of polymers, as a safety signal color and for the production of optical filters.

13. varnish from a solvent-containing, water-based, or a solvent and / or water-free binder and color bodies, characterized in that it contains an organic effect colorant of claim 1 or 7.

14. Printing ink or ink from a solvent-based, water-based, or from a solvent and / or water-free binder and color bodies, characterized in that it contains an organic effect colorant of claim 1 or 7.

15. Pasty or fluid, in particular spreadable, sprayable or pourable, preparations of solid phase 1 polymers in a melt or dispersion / emulsion of the phase 2 polymers or in one at normal temperature or only at elevated temperature. rature liquid substance mixture containing precursors of the phase 2 polymers, which can be converted into the phase 2 polymers.

16. Pasty or fluid preparation clay according to claim 15, characterized in that its viscosity is so low or can be reduced by simple measures to the extent that the phase 1 polymers can form at least domains of a regular arrangement.

17. Pasty or fluid preparation clay according to at least one of claims 15 and 16, characterized in that it contains 20 to 99% by weight, preferably 30 to 90% by weight, in particular 40 to 80% by weight of the dispersed phase 1 Polymers, and 1 to 80% by weight, preferably 10 to 70% by weight, in particular 20 to 60% by weight, of a fluid or pasty substance mixture which in turn contains 5 to 95% by weight, preferably 10 to 90 % By weight, in particular 20 to 70% by weight, of melted or dispersed phase 2 polymers or polymer precursors, and 95 to 5% by weight, preferably 90 to 10% by weight, in particular 80 to 30% by weight. -% of solvents, dispersants, auxiliaries and / or additives.

18. Solid preparations of the phase 1 polymers, comprising phase 1 polymers and the amount of phase 2 polymers in powder form required to form a continuous matrix or a corresponding amount of a mixture of substances which is solid at normal temperature and which is incorporated into the phase 2 Poly mers can be transferred.

19. Solid preparation clay according to claim 18, characterized in that it contains 20 to 99% by weight, preferably 40 to 95% by weight, in particular 60 to 90% by weight of the phase 1 polymers, and 1 to 80% by weight .-%, preferably 5 to 60 wt .-%, in particular 10 to 40 wt .-% of a solid substance mixture, which in turn 60 to 100 wt .-%, preferably 70 to 99 wt .-%, in particular 80 to 95 wt % meltable, dispersible or soluble phase 2 polymers or polymer precursors, and 0 to 40% by weight, preferably 1 to 30% by weight, in particular 5 to 20% by weight of auxiliaries and / or

Contains additives.

20. Use of the solid, fluid or pasty preparations for the production of decorative and / or protective coatings.

21. Powdery polymer material consisting essentially of particles of phase 1 polymers, the particles having a size of 0.05 to 5 μm, preferably 0.1 to 2 μm, in particular 0.15 to 1.0 μm and especially of 0.2 to 0.7 μm and a polydispersity index PI have less than 0.6, preferably less than 0.4, in particular less than 0.3.

22. Use of the powdery polymer material of claim 21 for the production of the multi-phase effect colorant of claim 1.

23. A process for the preparation of the multi-phase effect colorant of claim 1 comprising the following steps: a) Preparation of a suspension of one or more solid, non-swellable phase 1 polymers in a liquid mixture of Monomers, prepolymers or polymers of phase 2, if necessary a solvent, diluent in which solids belonging to phase 2 are dispersed, and optionally further auxiliaries, the monomer and polymer constituents being selected such that the

Hardening of the phase 2 polymers between phases 1 and 2 results in a difference in the refractive indices, b) application of the mixture prepared according to a) to a substrate, c) orientation of the phase 1 polymer particles to at least domains of regular structure, d) if necessary, allowing the solvent or diluent possibly contained in the applied layer to evaporate or e) and e) if necessary curing the film on the substrate, f) detaching the cured film from the substrate and g) if a pigment or powder is produced should, shredding the detached film to the desired particle size.

24. The method according to claim 23, characterized in that the disperse phase 1, optionally in a separate process step, is prepared by emulsion, suspension, microemulsion or microsuspension polymerization.

25. The method according to at least one of claims 23 and 24, characterized in that the application of the mixture according to process step b) is carried out on the substrate in the form of a plurality of small dots of the desired shape and size and the comminution step g) is facilitated or can be omitted.

26. The method according to at least one of claims 23 to 25, characterized in that step a) under

Use of a preparation of claim 15 or claim 18 or a powder of claim 21 is carried out.

27. Process for the production of decorative and / or protective

Coatings by applying a coating agent to the material to be protected, optionally pretreated, in a manner known per se, characterized in that a preparation of one of claims 15 or 18 is used as the coating agent.